Soft Heterogeneous Isotactic Polypropylene Compositions

ABSTRACT

Provided are heterogeneous blend compositions comprising; a) from 1% to 99% by weight of the blend of a first polymer component comprising a copolymer of 5% to 35% by weight of the first polymer component consisting predominantly of alpha olefin derived units and 65% to 95% by weight of the first polymer component of propylene derived units having a crystallinity of 0.1% to about 25% from isotactic polypropylene sequences, a melting point of from 45° C. to 105° C., and wherein the Melt Flow Rate (MFR@230 C) of the first polymer component is between 300 g/10 min to 5000 g/10 min b) from 1% to 99% by weight of the blend of a second polymer component comprising isotactic polypropylene and random copolymers of isotactic propylene, wherein the percentage of the copolymerized alpha-olefin in the copolymer is between 0.0% and 9% by weight of the second polymer component and wherein the second polymer component has a melting point greater than about 110° C., wherein the first polymer component has less than 1000 ppm of reaction products arising from the chemical reaction of a molecular degradation agent. The provided compositions are useful in high temperature applications.

PRIORITY CLAIM

This application claims priority to and the benefit of U.S. Ser. No.60/983,076, filed Oct. 26, 2007.

FIELD OF THE INVENTION

The invention relates to heterogeneous polymer blends of at least twopolymers having surprising properties when compared to the properties ofthe individual polymers prior to blending. More specifically, theinvention relates to blends of thermoplastic polymers, e.g., accordingto one embodiment, polypropylene and an olefin copolymer.

BACKGROUND OF THE INVENTION

Although blends of isotactic polypropylene and olefin copolymers arewell known in the prior art, prior art systems could not produce a goodbalance of flexural modulus, tensile strength and elasticity as afunction of the content of the olefin copolymer. There exists a need forpolymeric materials which have advantageous processing characteristicswhile still providing suitable end properties to articles formedtherefrom. Copolymers and blends of polymers have been developed to tryand meet the above needs. The present invention shows a surprising andunexpected balance of flexural modulus, tensile strength and elasticityas a function of the content of the alpha olefin. Moreover, these andother properties of the copolymers show surprising differences relativeto conventional polymer blends, such as blends of isotacticpolypropylene and propylene alpha olefin copolymers.

U.S. Pat. No. 4,178,272 describes hot-melt adhesives comprising athermally degraded crystalline polypropylene, a propylene/hexenecopolymer and a hydrocarbon resin.

U.S. Pat. No. 6,747,114 describes an adhesive composition that caninclude a semi-crystalline, preferably random, copolymer of propyleneand at least one comonomer selected from the group consisting ofethylene and at least one C4 to C20 α-olefin.

U.S. Pat. No. 6,635,715 describes thermoplastic polymer blendcompositions comprising an isotactic polypropylene component and anα-olefin/propylene copolymer component, said copolymer comprisingcrystallizable α-olefin sequences.

SUMMARY OF THE INVENTION

Provided are heterogeneous polymer blends of at least two polymers. Thepolymer blends are useful for high temperature applications such as, forexample, applications above 90° C. Even at elevated temperatures, theprovided polymer blends exhibit beneficial properties and may replaceoils with a polymer in various applications, including compoundingapplications, while reducing brittleness, lowering Tag and modulus,flexible flexibilizer, allowing higher solids and pigment loading,lowering torque and increases energy efficiency, permiting fasterprocessing speeds, and providing clarity for use with polypropylene.While exhibiting these properties at high temperature, the providedpolymer blends enable use of additional avenues of manufacturing andprocessing.

We have discovered that low molecular weight semicrystallinepropylene-ethylene copolymers (hereinafter the first polymer component)which contain isotactic propylene crystallinity, when produced in thepresence of a metallocene catalyst and an activator, in a single steadystate reactor, show a surprising and unexpected balance of flexuralmodulus, tensile strength and elasticity as a function of the content ofthe alpha olefin. Moreover, these and other properties of the copolymersshow surprising differences relative to conventional polymer blends,such as blends of isotactic polypropylene and propylene alpha olefincopolymers.

In one embodiment, the first polymer component includes from a lowerlimit of 5% or 6% or 8% or 10% by weight to an upper limit of 20% or 25%by weight ethylene-derived units, and from a lower limit of 75% or 80%by weight to an upper limit of 95% or 94% or 92% or 90% by weightpropylene-derived units, the percentages by weight based on the totalweight of propylene- and ethylene-derived units wherein the firstpolymer component has less than 1000 ppm of reaction products arisingfrom the chemical reaction of a molecular degradation agent. Alphaolefin may be present along with the ethylene as long as the compositionof the copolymer contains more of the ethylene compared to the alphaolefin by weight.

In another embodiment, the invention comprises a solution polymerizationprocess for making the above described semicrystalline ethylenepropylene copolymers (the first polymer component) by using particularcatalyst and activator combination that lead to similar molecularweights and lower crystallinity from polymerization using previouscatalyst and activator combinations.

The present invention also discloses a heterogeneous blend compositioncomprising; a) from 1% to 99% by weight of the blend of a first polymercomponent comprising a copolymer of 5% to 35% by weight of the firstpolymer component consisting predominantly of alpha olefin derived unitsand 65% to 95% by weight of the first polymer component of propylenederived units having a crystallinity of 0.1% to about 25% from isotacticpolypropylene sequences, a melting point of from 45° C. to 105° C., andwherein the Melt Flow Rate (MFR@230 C) of the first polymer component isbetween 300 g/10 min to 5000 g/10 min. b) from 1% to 99% by weight ofthe blend of a second polymer component comprising isotacticpolypropylene and random copolymers of isotactic propylene, wherein thepercentage of the copolymerized alpha-olefin in the copolymer is between0.0% and 9% by weight of the second polymer component and wherein thesecond polymer component has a melting point greater than about 110° C.,wherein the first polymer component has less than 1000 ppm of reactionproducts arising from the chemical reaction of a molecular degradationagent.

DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plot of the heat of fusion as determined by DSC versus theweight percent of ethylene for the first polymer components for apreferred embodiment of the invention.

FIG. 2 is a plot of the 1% secant flexural modulus for the blends of thecurrent invention compared to the known competitive products as well asprior art.

FIGS. 3 and 4A-4D are electron micrographs of the blends of the currentinvention.

FIG. 5 is the DMTA trace for an First Polymer Component (identical toF2.17), Second Polymer Component (S.5) and their blends.

FIGS. 6 and 7 are the DMTA trace for an First Polymer Component(identical to F2.17), Second Polymer Component (S.5) and their blendswith plasticizer P.

FIGS. 8 and 9 are the DMTA trace of the invention compared to the datafor a commercial sample.

DETAILED DESCRIPTION OF THE INVENTION

A detailed description will now be provided. Depending on the context,all references below to the “invention” may in some cases refer tocertain specific embodiments only. In other cases it will be recognizedthat references to the “invention” will refer to subject matter recitedin one or more, but not necessarily all, of the claims. Each of theinventions will now be described in greater detail below, includingspecific embodiments, versions and examples, but the inventions are notlimited to these embodiments, versions or examples, which are includedto enable a person having ordinary skill in the art to make and use theinventions when the information is combined with available informationand technology.

This invention relates to (1) the formation of a low molecular weightpropylene dominated copolymer (the first polymer component) whichcontains less than 1000 ppm residues derived from a moleculardegradation agents, (2) blends of these first polymer components withisotactic polypropylene, (3) the use of a metallocene catalyst andactivator which leads to the attainment of a low crystallinity for thefirst polymer component at modest levels of the ethylene in the firstpolymer component and (4) the use of these polymers to generate a classof soft, plasticized, heterogeneous high flow blends with isotacticpolypropylenes.

In one embodiment the invention relates to the formation of a lowmolecular weight propylene alpha olefin copolymer which has some or allof the below features:

-   (i) a melting point ranging from an upper limit of less than 110°    C., or less than 90° C., or less than 80° C., or less than 70° C.,    to a lower limit of greater than 25° C., or greater than 35° C., or    greater than 40° C., or greater than 45° C.;-   (ii) a triad tacticity as determined by carbon-13 nuclear magnetic    resonance (¹³C NMR) of greater than 75%, or greater than 80%, or    greater than 85%, or greater than 90%;-   (iii) a relationship of elasticity to 500% tensile modulus such    that;    -   Elasticity≦0.935 M+12, or    -   Elasticity≦0.935 M+6, or    -   Elasticity≦0.935 M,    -   where elasticity is in percent and M is the 500% tensile modulus        in megapascal (ii) a relationship of elasticity to 500% tensile        modulus such that;-   (iv) a heat of fusion ranging from a lower limit of greater than 1.0    joule per gram (J/g), or greater than 1.5 J/g, or greater than 4.0    J/g, or greater than 6.0 J/g, or greater than 7:0 J/g, to an upper    limit of less than 125 J/g, or less than 100 J/g, or less than 75    J/g, or less than 60 J/g, or less than 50 J/g, or less than 40 J/g,    or less than 30 J/g;-   (v) a tacticity index m/r ranging from a lower limit of 4 or 6 to an    upper limit of 8 or 10 or 12;-   (vi) a proportion of inversely inserted propylene units based on 2,1    insertion of propylene monomer in all propylene insertions, as    measured by ¹³C NMR, of greater than 0.5% or greater than 0.6%;-   (vii) a proportion of inversely inserted propylene units based on    1,3 insertion of propylene monomer in all propylene insertions, as    measured by ¹³C NMR, of greater than 0.05%, or greater than 0.06%,    or greater than 0.07%, or greater than 0.08%, or greater than    0.085%;-   (viii) an intermolecular tacticity such that at least 75% by weight    of the copolymer is soluble in two adjacent temperature fractions of    a thermal fractionation carried out in hexane in 8° C. increments,    where X is 75, or 80, or 85, or 90, or 95, or 97, or 99;-   (ix) a reactivity ratio product r₁r₂ of less than 1.5, or less than    1.3, or less than 1.0, or less than 0.8;-   (xi) a molecular weight distribution Mw/Mn ranging from a lower    limit of 1.5 or 1.8 to an upper limit of 40 or 20 or 10 or 5 or 3;-   (xii) a MFR@230 C of greater than 250 g/10 min, greater than 300    g/10 min, greater than 400 g/10 min, greater than 500 g/10 min,    greater than 600 g/10 min, greater than 750 g/10 min, greater than    1000 g/10 min, greater than 1300 g/10 min, greater than 1600 g/10    min, greater than 2000 g/10 min and/or less than 7500 g/10 min, less    than 6500 g/10 min, less than 5500 g/10 min, less than 4500 g/10    min, less than 3000 g/10 min and less than 2500 g/10 min:-   (xiii) a 500% tensile modulus of greater than 0.5 MPa, or greater    than 0.8 MPa, or greater than 1.0 MPa, or greater than 2.0 MPa.-   (xiv) A heat of fusion related to the ethylene content of the    polymer such that the ethylene content is less than    17.112×e^(−(0.0203(heat of fusion)))+3, less than    17.112×e^(−(0.0203(heat of fusion)))+2 or less than    17.112×e^(−(0.0203(heat of fusion)))+1.-   (xv) The copolymer be made in the presence of a bridged metallocene    catalyst, in a single steady-state reactor.-   (xvi) the present invention is directed to a process for producing    an predominantly alpha olefin-propylene copolymer having some or all    of the above-recited characteristics, by reacting a mixture of    monomers including alpha olefins and propylene in a steady-state    reactor under reactive conditions and in the presence of a bridged    metallocene catalyst.-   (xvii) the copolymer contains less than 10000 ppm or less than 5000    ppm or less than 3000 ppm, less than 2000 ppm or less than 1000 ppm    or less than 500 ppm or less than 250 ppm of a molecular degradation    agent or its reactor products for propylene dominated polymers.

In another embodiment which relates to the blends of the aforementionedcopolymer and isotactic polypropylene, the present invention discloses aheterogeneous blend composition comprising; a) from 1% to 99% by weightof the blend of a first polymer component. b) from 1% to 99% by weightof the blend of a second polymer component comprising random copolymersof propylene, wherein the percentage of the copolymerized ethylene andalpha-olefin in the copolymer is between 0.5 and 9% by weight of thesecond polymer component and wherein the second polymer component has amelting point greater than about 110° C. Such second polymer componentsare preferably known in the art as random copolymers (RCP).

In one embodiment, the present invention discloses a heterogeneous blendcomposition of a first polymer component and the isotactic polypropyleneor isotactic random copolymers of polypropylene portion of a secondpolymer component comprising; a) from 1% to 99% by weight of the blendof a first polymer component b) from 1% to 99% by weight of the blend ofa second polymer component comprising isotactic polypropylene orisotactic random copolymers of propylene and an elastomer dispersedwithin the second polymer component in particles less than 10 μm indiameter wherein the percentage of the copolymerized ethylene andalpha-olefin in the isotactic polypropylene or isotactic randomcopolymers of propylene is between 0.0% and 9% by weight of the secondpolymer component and wherein the second polymer component has a meltingpoint greater than about 110° C., and wherein the second polymercomponent comprises an inherently heterogeneous blends of isotacticpolypropylene with rubbers and elastomers. Such component blends, whichare described as the second polymer component are commonly known in theart as thermoplastic olefins (TPO), impact copolymer (ICP) andthermoplastic vulcanizates (TPV). These are commercially available asSantoprene, Uniprene, Nexprene and Vegaprene which are examples ofTPV's. They are commercially available as Softell, Adflex and Catalloyproducts which are examples of TPO's. The composition limitation of thesecond polymer component in this embodiment refers only to isotacticpolypropylene or isotactic random copolymers of propylene portion of theblend which is the second polymer component of this embodiment.

In another embodiment, the present invention discloses a heterogeneousblend composition comprising; a) from 1% to 20% by weight of the blendof a first polymer component, b) from 80% to 99% by weight of the blendof a second polymer component comprising isotactic polypropylene andrandom copolymers of iostactic polypropylene, wherein the percentage ofthe copolymerized ethylene and alpha-olefin in the copolymer is between0.0 and 9% by weight of the second polymer component and wherein thesecond polymer component has a melting point greater than about 110° C.,wherein the first polymer component has less than 1000 ppm of reactionproducts arising from the chemical reaction of a molecular degradationagent.

In one embodiment, the present invention discloses a Heterogeneous blendcomposition of a first polymer component and the isotactic polypropyleneor isotactic random copolymers of polypropylene portion of a secondpolymer component comprising; a) from 1% to 30% by weight of the blendof a first polymer, b) from 80% to 99% by weight of the blend of asecond polymer component comprising isotactic polypropylene or isotacticrandom copolymers of propylene and an elastomer dispersed within thesecond polymer component in particles less than 10 μm in diameterwherein the percentage of the copolymerized ethylene and alpha-olefin inthe isotactic polypropylene or isotactic random copolymers of propyleneis between 0.0% and 9% by weight of the second polymer component andwherein the second polymer component has a melting point greater thanabout 110° C., and wherein the second polymer component comprises aninherently heterogeneous blends of isotactic polypropylene with rubbersand elastomers. Such component blends, which are described as the secondpolymer component are commonly known in the art as thermoplastic olefins(TPO), impact copolymer (ICP) and thermoplastic vulcanizates (TPV).These are commercially available as Santoprene, Uniprene, Nexprene andVegaprene which are examples of TPV's. They are commercially availableas Softell, Adflex and Catalloy products which are examples of TPO's.The composition limitation of the second polymer component in thisembodiment refers only to isotactic polypropylene or isotactic randomcopolymers of propylene portion of the blend which is the second polymercomponent of this embodiment.

In another embodiment, the present invention discloses a heterogeneousblend composition comprising: a) from 20% to 99% by weight of the blendof a first polymer component, b) from 80% to 1% by weight of the blendof a second polymer component comprising random copolymers of propylene,wherein the percentage of the copolymerized ethylene and alpha-olefin inthe copolymer is between 0.0 and 9% by weight of the second polymercomponent and wherein the second polymer component has a melting pointgreater than about 110° C.

In another embodiment, the present invention discloses a heterogeneousblend composition comprising: a) from 20% to 99% by weight of the blendof a first polymer component, b) from 80% to 99% by weight of the blendof a second polymer component comprising random copolymers of propylene,wherein the percentage of the copolymerized ethylene and alpha-olefin inthe copolymer is between 2.0 and 9% by weight of the second polymercomponent and wherein the second polymer component has a melting pointgreater than about 110° C., and wherein the blend of the first polymercomponent and the second polymer component contains, in addition to theaforementioned components, a plasticizer.

In another embodiment, the present invention discloses a heterogeneousblend composition comprising: a) from 20% to 99% by weight of the blendof a first polymer component, b) from 80% to 99% by weight of the blendof a second polymer component comprising random copolymers of propylene,wherein the percentage of the copolymerized ethylene and alpha-olefin inthe copolymer is between 2.0 and 9% by weight of the second polymercomponent and wherein the second polymer component has a melting pointgreater than about 110° C., and wherein the blend of the first polymercomponent and the second polymer component contains, in addition to theaforementioned components, a plasticizer and where the final blend ofthe first polymer components, the second polymer component and theplasticizer satisfies the relationship.

1% secant Flex Modulus (kpsi)=−7.0963 Ln [(MFR g/10 min)₂×Tensilestrength0.5]+85.88. More preferably, 1% secant Flex Modulus(kpsi)=−7.0963 Ln [(MFR g/10 min)₂×Tensile strength0.5]+83.88. Morepreferably, 1% secant Flex Modulus (kpsi)=−7.0963 Ln [(MFR g/10min)₂×Tensile strength0.5]+80.88.

In another embodiment, the present invention discloses a heterogeneousblend composition comprising: a) from 20% to 99% by weight of the blendof a first polymer component, b) from 80% to 99% by weight of the blendof a second polymer component comprising random copolymers of propylene,wherein the percentage of the copolymerized ethylene and alpha-olefin inthe copolymer is between 2.0 and 9% by weight of the second polymercomponent and wherein the second polymer component has a melting pointgreater than about 110° C., wherein the MFR of the second polymercomponent is less than 10 g/10 min, and wherein the blend of the firstpolymer component and the second polymer component contains, in additionto the aforementioned components, a plasticizer and where the finalblend of the first polymer components, the second polymer component andthe plasticizer satisfies the relationship.

1% secant Flex Modulus (kpsi)=−7.0963 Ln [(MFR g/10 min)₂×Tensilestrength0.5]+85.88. More preferably, 1% secant Flex Modulus(kpsi)=−7.0963 Ln [(MFR g/10 min)₂×Tensile strength0.5]+83.88. Morepreferably, 1% secant Flex Modulus (kpsi)=−7.0963 Ln [(MFR g/10min)₂×Tensile strength0.5]+80.88.

In another embodiment the present invention discloses a heterogeneousblend composition comprising: a) from 1% to 99% by weight of the blendof a first polymer component, b) from 1% to 99% by weight of the blendof a second polymer component comprising random copolymers of propylene,wherein the percentage of the copolymerized ethylene and alpha-olefin inthe copolymer is between 0.0% and 9% by weight of the second polymercomponent and wherein the second polymer component has a melting pointgreater than about 110° C., and wherein a glass transition temperatureof said first polymer component is retained in the final blend.

It is understood that in the context of the any or all of the aboveembodiments the MFR of the second polymer component is less than 200g/10 min, less than 150 g/10 min, less than 100 g/10 min, less than 75g/10 min. less than 50 g/10 min, less than 30 g/10 min, less than 20g/10 min or preferably less than 10 g/10 min or less than 5 g/10 min orless than 3 g/10 min or less than 2 g/10 min.

It is understood that in the context of any or all of the aboveembodiments the polymer blend may contain added process oil. The processoil may consist of paraffinic oils, aromatic oils, oligomeric esters andethers as well as any other plasticizer commonly used for polyolefincompounds.

It is understood that in the context of any or all of the aboveembodiments the polymer blend may contain other various additives whichmay be present to enhance a specific property or may be present as aresult of processing of the individual components. These compounds mayinclude fillers and/or reinforcing materials. These include carbonblack, clay, talc, calcium carbonate, mica, silica, silicate,combinations thereof, and the like Additives which may be incorporatedinclude, for example, fire retardants, antioxidants, plasticizers,pigments, vulcanizing or curative agents, vulcanizing or curativeaccelerators, cure retarders, processing aids, flame retardants,tackifying resins, and the like. Other additives which may be employedto enhance properties include antiblocking agents, coloring agent.Lubricants, mold release agents, nucleating agents, reinforcements, andfillers (including granular, fibrous, or powder-like) may also beemployed.

It is understood that any or all of the above embodiments are directedto a process for preparing thermoplastic blends of the first and secondpolymer components is contemplated. The process comprises: (a)polymerizing propylene or a mixture of propylene and one or moremonomers selected from C₂ or C₃-C₂₀alpha olefins in the presence of apolymerization catalyst wherein a substantially isotactic propylenepolymer containing at least 90% by weight polymerized propylene isobtained; (b) polymerizing a mixture of ethylene and propylene in thepresence of a chiral metallocene catalyst, wherein a crystallizablecopolymer of ethylene and propylene is obtained comprising up to 35% byweight ethylene and preferably up to 20% by weight ethylene andcontaining isotactically crystallizable propylene sequences; and (c)blending the propylene polymer of step (a) with the crystallizablecopolymer of step (b) to form a blend. During the blending procedureplasticizers and inorganic filler are added. Prochiral catalystssuitable for the preparation of crystalline and semi-crystallinepolypropylene copolymers include those described in U.S. Pat. Nos.5,145,819; 5,304,614; 5,243,001; 5,239,022; 5,329,033; 5,296,434;5,276,208; 5,672,668; 5,304,614; and 5,374,752; and EP 549 900 and 576970, all fully incorporated herein by reference. Additionally,metallocenes such as those described in U.S. Pat. No. 5,510,502 (fullyincorporated herein by reference) are suitable for use in thisinvention. It is understood that any or all of the above embodiments isdirected to a process for preparing of thermoplastic fabricated ariclesfrom these thermoplastic polymer blends. The process comprises: (a)generating the thermoplastic blend (as described immediately above), (b)forming the thermoplastic article by casting, blowing, injectionmolding, extrusion, rotomolding or compression molding as described inthe art, (c) annealing the resulting article for a period of time lessthan 20 days at a temperature not to exceed 170° C. and (d) orientingthe article either uniaxially or biaxially by extension to not greaterthan 700% of its original dimension. The annealing and/or theorientation may be conducted in a single operation or as distinctivesequential operations.

It is understood that any or all of the above embodiments, including thecompositions and fabrication process the first polymer component mayinclude ethylene in addition to alpha olefin monomers containing between3 to 20 carbon atoms such as butene, hexene or octene. These arecollectively referred to as alpha olefins in this disclosure.Preferentially ethylene may be present in a quantity by weight more thanthat of the alpha olefins, preferentially more than two times the weightof the alpha olefin, preferentially more than three times the weight ofthe alpha olefin, and preferentially more than four times the weight ofthe alpha olefin. We believe that adding ethylene in a proportion morein weight compared to the alpha olefin leads to the formation of aheterogeneous blend of the first and the second polymer component.

The effects of this invention are exemplified by the properties of thecomposition. The creation of iPP based compositions which aresimultaneously both soft and easily moldable and yet have excellenttensile, elongation and tear strength has been a challenge. Thematerials of the current invention are tough and soft while still beingextremely fluid at the temperature needed for molding and fabrication.In this application:

-   -   Soft indicates compositions with a flex modulus (1% secant) of        less than 45 kpsi, preferably less than 35 kpsi, preferably less        than 25 kpsi and even more preferably less than 15 kpsi.    -   Easily moldable means simultaneously (1) a MFR@230 C greater        than 50 g/10 min, preferably greater than 80 g/10 min,        preferably greater than 100 g/10 min and most preferably greater        than 150 g/10 min and (2) a crystallization temperature greater        than 60 C, preferably greater than 75 C and even more preferably        greater than 90 C.    -   High Tensile strength means an ultimate tensile strength greater        than 500 psi, preferably greater than 700 psi and more        preferably greater than 1000 psi.

High elongation means that the elongation to failure should be greaterthan 100%, preferably greater than 200% and more preferably greater than300%.

High Die C tear means that the Die C tear is greater than 150 lb/in,preferably greater than 225 lb/in and more preferably greater than 300lb/in.

In the above discussion the above numerical limits are advisory and notcorrelated. Thus is within the realm of the invention to conceive of aninventive composition which is deficient in some of the parameters whilesurpassing the values in all or most of the others.

The provided compositions may be used in compounded applications. Incompounds, the provided compositions lead to improved processing asnoted by a lowering of the viscosity without a significant orunacceptable compromise of the physical properties. Compounding is aprocess where polymeric ingredients, fillers, plasticizers comprisingthe classes and examples indicated below are mixed together to form ahomogeneous mixture. It is understood that in the context of any or allof the above embodiments the polymer blend may contain other variousadditives which may be present to enhance a specific property or may bepresent as a result of processing of the individual components. Thesecompounds may include fillers and/or reinforcing materials. Theseinclude carbon black, clay, talc, calcium carbonate, mica, silica,silicate, combinations thereof, and the like Additives which may beincorporated include, for example, fire retardants, antioxidants,plasticizers, pigments, vulcanizing or curative agents, vulcanizing orcurative accelerators, cure readers, processing aids, flame retardants,tackifying resins, and the like. Other additives which may be employedto enhance properties include antiblocking agents, coloring agent.Lubricants, mold release agents, nucleating agents, reinforcements, andfillers (including granular, fibrous, or powder-like) may also beemployed.

The provided compositions may be fabricated by a variety of proceduresenumerated below. These include injection molding, compression molding,rotational molding, blow molding, thermoforming and extrusion. Moldingis a process for fabrication whereby the molten plastic or thermoplasticis injected of formed at high pressure into a mold which is the inverseof the product's shape. Molding is widely used for manufacturing avariety of parts, from the smallest component to entire body panels ofcars. Injection molding is the most common method of production, withsome commonly made items including bottle caps and outdoor furniture.

Extrusion is an alternate form of fabrication where the moltenthermoplastic is ejected through a forming die. The die imparts a twodimensional shape to the plastic which exits and is rapidly cooled tomaintain the shape. Extrusion molding is used for sheets, rods, tubersand profiles such as door gaskets where long pieces with an invariantcross section are required.

These provided compositions can also be formed into membranes and filmsby calendaring. In the calendaring process the thermoplastic is extrudedat high pressure through a uniform long slit die or the gap of acalendar. The resultant fabrication is a uniform sheet of membrane whichretains the cross section of the die. An alternate fabrication processfor the formation of the films or membranes is a blown film processwhere a film is generated and collected by extrusion through a circularannular die. The resultant circular sheet, i.e., a bubble, can bedimensionally modified by an in increase in the internal air pressurewhich leads to uniform distension of the sheet prior to collectionleading to a smooth sheet.

These low viscosity compositions, in addition to these plasticfabrication processes, can also be fabricated into coatings andlaminates by pouring or applying a thin uniform sheet of thethermoplastic compound as made in one of more of the several processesdescribed above to a cloth, canvas, plastic sheet substrate. Thesecoating or laminations are useful for textile coatings and thegeneration of waterproof fabrics. The coating may be applied by sprayingpumping or pouring the thermoplastic onto the sheet. One of more sheetsmay be used in any of the above process to form laminations of the softthermoplastic between two sheets. That application may be by spraying,pumping or uniformly pouring this compound on the sheet like substrate.This application may also be done in a calendar where the softthermoplastic can be forced into the crevices and the surface of thesheet.

In addition the provided compositions can also be applied to the sheetsusing a spray jet printer, in the same manner as spray on ink jetprinter. It is possible to contemplate the use of this inventivematerial in different colors to yield a multi color coating of thesheets by the ink jet printing process to lead to colorful andeconomical coatings for these sheets.

Injection molding, compression molding, rotational molding, blowmolding, thermoforming can be used for the fabrication of collapsiblestorage containers, garbage containers, food containers, recreation andsporting goods, grips for pens, razors, toothbrushes, handles, keypads,syringe plunger tips, synthetic wine corks. Shoe soles, bumper fasciaand instrument panel and trim skin for automotive uses as well as forArchitectural structures. These are illustrative uses only, andsignificant other known uses are contemplated.

For example, calendaring and sheet formation is used for single anddouble ply roofing, TPO roofing, light weight conveyor belt facing,belting awnings and canopies, tents/tarps, covers, curtains, extrudedsoft sheet, protective cloth coated fabric, coated fabric for autointerior and geo textiles. In addition these sheets can be fabricated toform intravenous and fluid administration bags and examination gloves.

Extrusion of these compositions can lead to appliance door gaskets,liners/gaskets/mats and hose and tubing.

In general the use of the provided compositions replaces oil with apolymer, reduces brittleness, lowers Tag and modulus, flexibleflexibilizer, allows higher solids and pigment loading, lowers torqueand increases energy efficiency, permits faster processing speeds,provides clarity for use with PP.

As shown in FIGS. 5-9, specifically identified compositions exhibitbeneficial properties. As shown in these figures the providedcompositions exhibit beneficial performance above about 90° C., or aboveabout 100° C., or above about 110° C., or above about 125° C.

First Polymer Component:

The first polymer component of the polymer blend compositions of thepresent invention comprises a crystallizable copolymer of propylene andethylene with optional small amounts of alpha olefins with the followingcharacteristics. A crystallizable polymer is defined as, which isdistinct from a crystalline polymer, a polymeric component where themeasured crystallinity of the polymer as measured by the heat of fusionby DSC, as described in the procedure below, is augmented at least by afactor of at least 1.5, or at least 2 by either waiting for a period of120 hours at room temperature, by singly or repeatedly mechanicaldistending the sample or by contact with the second polymer component,which is described in more detail below. In one embodiment the inventionrelates to the formation of a low molecular weight propylene alphaolefin copolymer which has some or all of the below features.

Composition:

The copolymer (first polymer component) includes from a lower limit of5% or 6% or 8% or 10% by weight ethylene-derived units to an upper limitof 20% or 25% by weight ethylene-derived units. These embodiments alsowill include propylene-derived units present in the copolymer in therange of from a lower limit of 75% or 80% by weight to an upper limit of95% or 94% or 92% or 90% by weight. These percentages by weight arebased on the total weight of the propylene and ethylene-derived units;i.e., based on the sum of weight percent propylene-derived units andweight percent ethylene-derived units being 100%. Within these ranges,these copolymers are mildly crystalline as measured by differentialscanning calorimetry (DSC), and are exceptionally soft, while stillretaining substantial tensile strength and elasticity. Elasticity, asdefined in detail herein below, is a dimensional recovery fromelongation for these copolymers. At ethylene compositions lower than theabove limits for the copolymer, such polymers are generally crystalline,similar to crystalline isotactic polypropylene, and while havingexcellent tensile strength, they do not have the favorable softness andelasticity. At ethylene compositions higher than the above limits forthe copolymer component, the copolymer is substantially amorphous.Notwithstanding this compositional limitation on the first polymercomponent it is anticipated that it may in addition to propylene andethylene also contain small amounts of one or more higher alpha olefinsas long as the final blend of the first and the second polymer componentis heterogeneous in morphology. Higher alpha olefins are those that have3 or more carbon atoms and preferably less than 20 carbon atoms. It isbelieved, while not meant to be limited thereby, the first polymercomponent needs to have the optimum amount of polypropylenecrystallinity to crystallize with the second polymer component for thebeneficial effects of the present invention. While such a material ofhigher ethylene composition may be soft, these compositions are weak intensile strength and poor in elasticity. In summary, such copolymers ofembodiments of our invention exhibit the softness, tensile strength andelasticity characteristic of vulcanized rubbers, without vulcanization.

We intend that the copolymer (first Polymer component) may includediene-derived units. Dienes are nonconjugated diolefins which may beincorporated in polymers to facilitate chemical crosslinking reactions.May include diene” is defined to be greater than 1% diene, or greaterthan 0.5% diene, or greater than 0.1% diene. All of these percentagesare by weight in the copolymer. The presence or absence of diene can beconventionally determined by infrared techniques well known to thoseskilled in the art. Sources of diene include diene monomer added to thepolymerization of ethylene and propylene, or use of diene in catalysts.No matter the source of such dienes, the above outlined limits on theirinclusion in the copolymer are contemplated. Conjugated diene-containingmetallocene catalysts have been suggested for the formation ofcopolymers of olefins. However, polymers made from such catalysts willincorporate the diene from the catalyst, consistent with theincorporation of other monomers in the polymerization.

Sequence of Comonomers

The first polymer component of the present invention preferablycomprises a random copolymer having a narrow crystallinity distribution.While not meant to be limited thereby, it is believed that the narrowcrystallinity distribution of the first polymer component is important.The intermolecular composition distribution of the polymer is determinedby thermal fractionation in a solvent. A typical solvent is a saturatedhydrocarbon such as hexane or heptane. The thermal fractionation of thepolymer is conducted by exposing a sample of the first polymer componentto heptane at 50° C. with slight intermittent agitation. The polymer hasa narrow distribution of crystallinity if no more than 25%, morepreferably no more than 10% and yet more preferably no more than 5% ofthe first polymer component is insoluble after 48 hours.

The first polymer component, the length and distribution ofstereoregular propylene sequences is consistent with the substantiallyrandom statistical copolymerization. It is well known that sequencelength and distribution are related to the copolymerization reactivityratios. A substantially random copolymer is a copolymer for which theproduct of the reactivity ratios is 2 or less. In stereoblockstructures, the average length of PP sequences is greater than that ofsubstantially random copolymers with a similar composition. Prior artpolymers with stereoblock structure have a distribution of PP sequencesconsistent with these blocky structures rather than a randomsubstantially statistical distribution. The reactivity ratios andsequence distribution of the polymer may be determined by C-13 NMR whichlocates the comonomer residues in relation to the neighboring propyleneresidues. To produce a copolymer with the required randomness and narrowcomposition distribution, it is desirable to use (1) a single sitedcatalyst and (2) a well-mixed, continuous flow stirred tankpolymerization reactor which allows only a uniform polymerizationenvironment for growth of substantially all of the polymer chains of thesecond polymer component.

The first polymer component has stereoregular propylene sequences longenough to crystallize. These stereoregular propylene sequences of thefirst polymer component may match the stereoregularity of the propylenein the second polymer component. For example, if the second polymercomponent is predominately isotactic polypropylene, then the firstpolymer component if used, are copolymers having isotactic propylenesequences. If the second polymer component is predominately syndiotacticpolypropylene, then first polymer component is a copolymer havingsyndiotactic sequences. It is believed that this matching ofstereoregularity increases the compatibility of the components resultsin improved solubility and compatibility of the polymers of differentcrystallinities in the polymer blend composition. The aforementionedcharacteristics of the first polymer component are preferably achievedby polymerization with a chiral metallocene catalyst. In a furtherembodiment, the first polymer component of the present inventivecomposition comprises crystallizable propylene sequences.

One method to describe the molecular features of an ethylene-propylenecopolymer is monomer sequence distribution. Starting with a polymerhaving a known average composition, the monomer sequence distributioncan be determined using spectroscopic analysis. Carbon 13 nuclearmagnetic resonance spectroscopy (¹³C NMR) can be used for this purpose,and can be used to establish diad and triad distribution via theintegration of spectral peaks. (If ¹³C NMR is not used for thisanalysis, substantially lower r₁r₂ products are normally obtained.) Thereactivity ratio product is described more fully in Textbook of PolymerChemistry, F. W. Billmeyer, Jr., Interscience Publishers, New York, p.221 et seq. (1957).

The reactivity ratio product r₁r₂, where r₁ is the reactivity ofethylene and r₂ is the reactivity of propylene, can be calculated fromthe measured diad distribution (PP, EE, EP and PE in this nomenclature)by the application of the following formulae:

r ₁ r ₂=4(EE)(PP)/(EP)²

r ₁ =K ₁₁ /K ₁₂=[2(EE)/EP]X

r ₂ =K ₂₂ /K ₂₁=[2(PP)/(EP)]X

P=(PP)+(EP/2)

E=(EE)+(EP/2)

where

Mol % E=[(E)/(E+P)]*100

X=E/P in reactor;

K₁₁ and K₁₂ are kinetic insertion constants for ethylene; and

K₂₁ and K₂₂ are kinetic insertion constants for propylene.

As is known to those skilled in the art, a reactivity ratio product r₁r₂of 0 can define an “alternating” copolymer, and a reactivity ratioproduct of 1 is said to define a “statistically random” copolymer. Inother words, a copolymer having a reactivity ratio product r₁r₂ ofbetween 0.6 and 1.5 is generally said to be random (in stricttheoretical terms, generally only a copolymer having a reactivity ratioproduct r₁r₂ greater than 1.5 contains relatively long homopolymersequences and is said to be “blocky”). The copolymer of our inventionwill have a reactivity ratio product r₁r₂ of less than 1.5, or less than1.3, or less than 1.0, or less than 0.8. The substantially uniformdistribution of comonomer within polymer chains of embodiments of ourinvention generally precludes the possibility of significant amounts ofpropylene units or sequences within the polymer chain for the molecularweights (weight average) disclosed herein.

Stereoregularity

The first polymer component is made with a polymerization catalyst whichforms essentially or substantially isotactic polypropylene when all orsubstantially all propylene sequences in the second polypropylene areisotactic. Nonetheless, the polymerization catalyst used for theformation of the first polymer component will introduce stereo- andregio-errors in the incorporation of propylene. Stereo errors are thosewhere the propylene inserts in the chain with a tacticity that is notisotactic and the orientation of the adjacent methyl groups is not meso.A regio error of one kind in one where the propylene inserts with themethylene group or the methyldiene group adjacent to a similar group inthe propylene inserted immediately prior to it. A regio error of anotherkind is one where a propylene inserts in a 1,3 insertion instead of themore usual 1,2 insertion. Such errors are more prevalent after theintroduction of a comonomer in the first polymer component. Thus, thefraction of propylene in isotactic stereoregular sequences (e.g. triadsor pentads) is less than 1 for the first polymer component and decreaseswith increasing comonomer content of the first polymer component. Whilenot wanting to be constrained by this theory, the introduction of theseerrors in the introduction of propylene, particularly in the presence ofincreasing amounts of comonomer, are important in the use of thesepropylene copolymers as the first polymer component. Notwithstanding thepresence of these errors, the first polymer component is statisticallyrandom in the distribution of comonomer.

Triad Tacticity

An ancillary procedure for the description of the tacticity of thepropylene units of embodiments of the current invention is the use oftriad tacticity. The triad tacticity of a polymer is the relativetacticity of a sequence of three adjacent propylene units, a chainconsisting of head to tail bonds, expressed as a binary combination of mand r sequences. It is usually expressed for copolymers of the presentinvention as the ratio of the number of units of the specified tacticityto all of the propylene triads in the copolymer.

The triad tacticity (mm fraction) of a propylene copolymer can bedetermined from a ¹³C NMR spectrum of the propylene copolymer and thefollowing formula:

where PPP(mm), PPP(mr) and PPP(rr) denote peak areas derived from themethyl groups of the second units in the following three propylene unitchains consisting of head-to-tail bonds:The ¹³C NMR spectrum of the propylene copolymer is measured as describedin U.S. Pat. No. 5,504,172. The spectrum relating to the methyl carbonregion (19-23 parts per million (ppm)) can be divided into a firstregion (21.2-21.9 ppm), a second region (20.3-21.0 ppm) and a thirdregion (19.5-20.3 ppm). Each peak in the spectrum was assigned withreference to an article in the journal Polymer, Volume 30 (1989), page1350.

In the first region, the methyl group of the second unit in the threepropylene unit chain represented by PPP (mm) resonates.

In the second region, the methyl group of the second unit in the threepropylene unit chain represented by PPP (mr) resonates, and the methylgroup (PPE-methyl group) of a propylene unit whose adjacent units are apropylene unit and an ethylene unit resonates (in the vicinity of 20.7ppm).

In the third region, the methyl group of the second unit in the threepropylene unit chain represented by PPP (rr) resonates, and the methylgroup (EPE-methyl group) of a propylene unit whose adjacent units areethylene units resonates (in the vicinity of 19.8 ppm).

Calculation of the Triad Tacticity and Errors in Propylene Insertion

The calculation of the triad tacticity is outlined in the techniquesshown in U.S. Pat. No. 5,504,172. Subtraction of the peak areas for theerror in propylene insertions (both 2,1 and 1,3) from peak areas fromthe total peak areas of the second region and the third region, the peakareas based on the 3 propylene units-chains (PPP(mr) and PPP(rr))consisting of head-to-tail bonds can be obtained. Thus, the peak areasof PPP(mm), PPP(mr) and PPP(rr) can be evaluated, and hence the triadtacticity of the propylene unit chain consisting of head-to-tail bondscan be determined.

The propylene copolymers of embodiments of our invention have a triadtacticity of three propylene units, as measured by ¹³C NMR, of greaterthan 75%, or greater than 80%, or greater than 82%, or greater than 85%,or greater than 90%.

Stereo- and Regio-Errors in Insertion of Propylene: 2,1 and 1,3Insertions

The insertion of propylene can occur to a small extent by either 2,1(tail to tail) or 1,3 insertions (end to end). Examples of 2,1 insertionare shown in structures 1 and 2 below.

where n≧2.

A peak of the carbon A and a peak of the carbon A′ appear in the secondregion. A peak of the carbon B and a peak of the carbon B′ appear in thethird region, as described above. Among the peaks which appear in thefirst to third regions, peaks which are not based on the 3 propyleneunit chain consisting of head-to-tail bonds are peaks based on thePPE-methyl group, the EPE-methyl group, the carbon A, the carbon A′, thecarbon B, and the carbon B′.

The peak area based on the PPE-methyl group can be evaluated by the peakarea of the PPE-methine group (resonance in the vicinity of 30.8 ppm),and the peak area based on the EPE-methyl group can be evaluated by thepeak area of the EPE-methine group (resonance in the vicinity of 33.1ppm). The peak area based on the carbon A can be evaluated by twice asmuch as the peak area of the methine carbon (resonance in the vicinityof 33.9 ppm) to which the methyl group of the carbon B is directlybonded; and the peak area based on the carbon A′ can be evaluated by thepeak area of the adjacent methine carbon (resonance in the vicinity of33.6 ppm) of the methyl group of the carbon B′. The peak area based onthe carbon B can be evaluated by the peak area of the adjacent methinecarbon (resonance in the vicinity of 33.9 ppm); and the peak area basedon the carbon B′ can be also evaluated by the adjacent methine carbon(resonance in the vicinity of 33.6 ppm).

By subtracting these peak areas from the total peak areas of the secondregion and the third region, the peak areas based on the three propyleneunit chains (PPP(mr) and PPP(rr)) consisting of head-to-tail bonds canbe obtained. Thus, the peak areas of PPP(mm), PPP(mr) and PPP(rr) can beevaluated, and the triad tacticity of the propylene unit chainconsisting of head-to-tail bonds can be determined.

The proportion of the 2,1-insertions to all of the propylene insertionsin a propylene elastomer was calculated by the following formula withreference to article in the journal Polymer, vol. 30 (1989), p. 1350.

Proportion of inversely inserted unit based on 2,1-insertion (%)=

Naming of the peaks in the above formula was made in accordance with amethod by Carman, et al. in the journal Rubber Chemistry and Technology,Vol. 44 (1971), pg. 781, where I_(αδ) denotes a peak area of the αδ⁺secondary carbon peak. It is difficult to separate the peak area of Iαβ(structure (i)) from Iαβ (structure (ii)) because of overlapping of thepeaks. Carbon peaks having the corresponding areas can be substitutedtherefor.

The measurement of the 1,3 insertion requires the measurement of the βγpeak. Two structures can contribute to the βγ peak: (1) a 1,3 insertionof a propylene monomer; and (2) from a 2,1-insertion of a propylenemonomer followed by two ethylene monomers. This peak is described as the1.3 insertion peak and we use the procedure described in U.S. Pat. No.5,504,172, which describes this βγ peak and understand it to represent asequence of four methylene units. The proportion (%) of the amount ofthese errors was determined by dividing the area of the βγ peak(resonance in the vicinity of 27.4 ppm) by the sum of all the methylgroup peaks and ½ of the area of the βγ peak, and then multiplying theresulting value by 100. If an α-olefin of three or more carbon atoms ispolymerized using an olefin polymerization catalyst, a number ofinversely inserted monomer units are present in the molecules of theresultant olefin polymer. In polyolefins prepared by polymerization ofα-olefins of three or more carbon atoms in the presence of a chiralmetallocene catalyst, 2,1-insertion or 1,3-insertion takes place inaddition to the usual 1,2-insertion, such that inversely inserted unitssuch as a 2,1-insertion or a 1,3-insertion are formed in the olefinpolymer molecule (see, Macromolecular Chemistry Rapid Communication,Vol. 8, pg. 305 (1987), by K. Soga, T. Shiono, S. Takemura and W.Kaminski).

The proportion of inversely inserted propylene units of embodiments ofour invention, based on the 2,1-insertion of a propylene monomer in allpropylene insertions, as measured by ¹³C NMR, is greater than 0.5%, orgreater than 0.6%.

The proportion of inversely inserted propylene units of embodiments ofour invention, based on the 1,3-insertion of a propylene monomer, asmeasured by ¹³C NMR, is greater than 0.05%, or greater than 0.06%, orgreater than 0.07%, or greater than 0.08%, or greater than 0.085percent.

InterMolecular Structure Homogeneous Distribution

Homogeneous distribution is defined as a statistically insignificantintermolecular difference of both in the composition of the copolymerand in the tacticity of the polymerized propylene. For a copolymer tohave a homogeneous distribution it must meet the requirement of twoindependent tests: (i) intermolecular distribution of tacticity; and(ii) intermolecular distribution of composition, which are describedbelow. These tests are a measure of the statistically insignificantintermolecular differences of tacticity of the polymerized propylene andthe composition of the copolymer, respectively.

Intermolecular Distribution of Tacticity

The copolymer of embodiments of our invention has a statisticallyinsignificant intermolecular difference of tacticity of polymerizedpropylene between different chains (intermolecularly.). This isdetermined by thermal fractionation by controlled dissolution generallyin a single solvent, at a series of slowly elevated temperatures. Atypical solvent is a saturated hydrocarbon such as hexane or heptane.These controlled dissolution procedures are commonly used to separatesimilar polymers of different crystallinity due to differences inisotactic propylene sequences, as shown in the article inMacromolecules, Vol. 26, pg. 2064 (1993). For the copolymers ofembodiments of our invention where the tacticity of the propylene unitsdetermines the extent of crystallinity, we expected this fractionationprocedure will separate the molecules according to tacticity of theincorporated propylene. This procedure is described below.

In embodiments of our invention, at least 75% by weight, or at least 80%by weight, or at least 85% by weight, or at least 90% by weight, or atleast 95% by weight, or at least 97% by weight, or at least 99% byweight of the copolymer is soluble in a single temperature fraction, orin two adjacent temperature fractions, with the balance of the copolymerin immediately preceding or succeeding temperature fractions. Thesepercentages are fractions, for instance in hexane, beginning at 23° C.and the subsequent fractions are in approximately 8° C. increments above23° C. Meeting such a fractionation requirement means that a polymer hasstatistically insignificant intermolecular differences of tacticity ofthe polymerized propylene.

Fractionations have been done where boiling pentane, hexane, heptane andeven di-ethyl ether are used for the fractionation. In such boilingsolvent fractionations, polymers of embodiments of our invention will betotally soluble in each of the solvents, offering no analyticalinformation. For this reason, we have chosen to do the fractionation asreferred to above and as detailed herein, to find a point within thesetraditional fractionations to more fully describe our polymer and thesurprising and unexpected insignificant intermolecular differences oftacticity of the polymerized propylene.

Intermolecular Composition and Tacticity Distribution Determination

Intermolecular composition distribution of the copolymer is measured asdescribed below. Nominally 30 grams of the copolymer is cut into smallcubes with about ⅛″ (3 mm) sides. This is introduced into a thick-walledglass bottle with a screw cap closure, along with 50 mg of Irganox 1076,an antioxidant commercially available from Ciba-Geigy Corporation. Then,425 mL of hexane (a principal mixture of normal and iso isomers) isadded to the bottle and the sealed bottle is maintained at 23° C. for 24hours. At the end of this period, the solution is decanted and theresidue is treated with additional hexane for an additional 24 hours. Atthe end of this period, the two hexane solutions are combined andevaporated to yield a residue of the polymer soluble at 23° C. To theresidue is added sufficient hexane to bring the volume to 425 mL and thebottle is maintained at 31° C. for 24 hours in a covered circulatingwater bath. The soluble polymer is decanted and an additional amount ofhexane is added for another 24 hours at 31° C. prior to decanting. Inthis manner, fractions of the copolymers soluble at 40° C., 48° C., 55°C. and 62° C. are obtained at temperature increases of approximately 8°C. between stages. Increases in temperature to 95° C. can beaccommodated if heptane, instead of hexane, is used as the solvent forall temperatures above about 60° C. The soluble polymers are dried,weighed and analyzed for composition, as wt. % ethylene content, by theIR technique described above. Soluble fractions obtained in the adjacenttemperature fractions are the adjacent fractions in the specificationabove.

Intermolecular Distribution of Composition

The copolymer of embodiments of our invention has statisticallyinsignificant intermolecular differences of composition, which is theratio of propylene to ethylene between different chains(intermolecular). This compositional analysis is by infraredspectroscopy of the fractions of the polymer obtained by the controlledthermal dissolution procedure described above.

A measure of the statistically insignificant intermolecular differencesof composition, each of these fractions has a composition (wt. %ethylene content) with a difference of less than 1.5 wt. % (absolute) orless than 1.0 wt. % (absolute), or less than 0.8 wt. % (absolute) of theaverage wt. % ethylene content of the whole copolymer. Meeting such afractionation requirement means that a polymer has statisticallyinsignificant intermolecular differences of composition, which is theratio of propylene to ethylene.

Intramolecular Distribution of Tacticity

The copolymer of embodiments of our invention has statisticallyinsignificant intramolecular differences of tacticity, which is due toisotactic orientation of the propylene units along the segments of thesame chain (intramolecular). This compositional analysis is inferredfrom the detailed analysis of the differential scanning calorimetry,electron microscopy and relaxation measurement (T_(1ρ)). In the presenceof significant intramolecular differences in tacticity, we would form‘stereoblock’ structures, where the number of isotactic propyleneresidues adjacent to one another is much greater than statistical.Further, the melting point of these polymers depends on thecrystallinity, since the more blocky polymers should have a highermelting point as well as depressed solubility in room temperaturesolvents.

Uniformity

Uniformity is defined to be a statistically insignificant intramoleculardifference of both the composition of the copolymer and in the tacticityof the polymerized propylene. For a copolymer to be uniform it must meetthe requirement of two independent tests: (i) intramoleculardistribution of tacticity; and (ii) intramolecular distribution ofcomposition, which are described below. These tests are a measure of thestatistically insignificant intramolecular differences of tacticity ofthe polymerized propylene and the composition of the copolymer,respectively.

Intramolecular Distribution of Composition

The copolymer of embodiments of our invention has statisticallyinsignificant intramolecular differences of composition, which is theratio of propylene to ethylene along the segments of the same chain(intramolecular). This compositional analysis is inferred from theprocess used for the synthesis of these copolymers as well as theresults of the sequence distribution analysis of the copolymer, formolecular weights in the range of from 15,000-5,000,000 or20,000-1,000,000.

Melting Point and Crystallinity

The first polymer component has a single melting point. The meltingpoint is determined by DSC. The first polymer component has a meltingpoint ranging from an upper limit of less than 110° C., or less than 90°C., or less than 80° C., or less than 70° C., to a lower limit ofgreater than 25° C., or greater than 35° C., or greater than 40° C., orgreater than 45°. Generally, the first polymer component of the presentinvention has a melting point between about 105° C. and 0° C.Preferably, the melting point is between about 90° C. and 20° C. Mostpreferably, the first polymer component has a heat of fusion rangingfrom a lower limit of greater than 1.0 joule per gram (J/g), or greaterthan 1.5 J/g, or greater than 4.0 J/g, or greater than 6.0 J/g, orgreater than 7:0 J/g, to an upper limit of less than 125 J/g, or lessthan 100 J/g, or less than 75 J/g, or less than 60 J/g, or less than 50J/g, or less than 40 J/g, or less than 30 J/g. Without wishing to bebound by theory, we believe that the copolymers of embodiments of ourinvention have generally isotactic crystallizable propylene sequences,and the above heats of fusion are believed to be due to the melting ofthese crystalline segments.

In another embodiment, the copolymers of the invention have a heat offusion that can be calculated by application of the following formula:

H _(f)>311*(E−18.5)² /T

Wherein:

-   -   H_(f)=the heat of fusion, measured as described below    -   E=the ethylene content (meaning units derived from ethylene) of        the copolymer, measured as described below; and is the        polymerization temperature of the first polymer component.

Molecular Weight and Polydispersity Index

Molecular weight distribution (MWD) is a measure of the range ofmolecular weights within a given polymer sample. It is well known thatthe breadth of the MWD can be characterized by the ratios of variousmolecular weight averages, such as the ratio of the weight averagemolecular weight to the number average molecular weight, Mw/Mn, or theratio of the Z-average molecular weight to the weight average molecularweight, Mz/Mw.

Mz, Mw and Mn can be measured using gel permeation chromatography (GPC),also known as size exclusion chromatography (SEC). This techniqueutilizes an instrument containing columns packed with porous beads, anelution solvent, and detector in order to separate polymer molecules ofdifferent sizes. In a typical measurement, the GPC instrument used is aWaters chromatograph equipped with ultrastyro gel columns operated at145° C. The elution solvent used is trichlorobenzene. The columns arecalibrated using sixteen polystyrene standards of precisely knownmolecular weights. A correlation of polystyrene retention volumeobtained from the standards, to the retention volume of the polymertested yields the polymer molecular weight.

Average Molecular Weights M can be Computed from the Expression:where N_(i) is the number of molecules having a molecular weight M_(i).When n=0, M is the number average molecular weight Mn. When n=1, M isthe weight average molecular weight Mw. When n=2, M is the Z-averagemolecular weight Mz. The desired MWD function (e.g., Mw/Mn or Mz/Mw) isthe ratio of the corresponding M values. Measurement of M and MWD iswell known in the art and is discussed in more detail in, for example,Slade, P. E. Ed., Polymer Molecular Weights Part II, Marcel Dekker,Inc., NY, (1975) 287-368; Rodriguez, F., Principles of Polymer Systems3rd ed., Hemisphere Pub. Corp., NY, (1989) 155-160; U.S. Pat. No.4,540,753; Verstrate et al., Macromolecules, Vol. 21, (1988) pg. 3360;and references cited therein.

In embodiments of our invention, a copolymer is included having a weightaverage molecular weight (Mw) of from 10,000-50,000, or from 20,000 to1,000,000 and a molecular weight distribution Mw/Mn [sometimes referredto as a “polydispersity index” (PDI)] ranging from a lower limit of 1.5or 1.8 to an upper limit of 40 or 20 or 10 or 5 or 3.

Melt Flow Rate at 230 C

The first polymer component has a MFR@230 C of greater than 250 g/10min, greater than 300 g/10 min, greater than 400 g/10 min, greater than500 g/10 min, greater than 600 g/10 min, greater than 750 g/10 min,greater than 1000 g/10 min, greater than 1300 g/10 min, greater than1600 g/10 min, greater than 2000 g/10 min and/or less than 7500 g/10min, less than 6500 g/10 min, less than 5500 g/10 min, less than 4500g/10 min, less than 3000 g/10 min and less than 2500 g/10 min.

Process of Manufacture

The polymerization process is a single stage, steady state,polymerization conducted in a well-mixed continuous feed polymerizationreactor. The polymerization can be conducted in solution, although otherpolymerization procedures such as gas phase or slurry polymerization,which fulfill the requirements of single stage polymerization andcontinuous feed reactors, are contemplated.

The process can be described as a continuous, non-batch process that, inits steady state operation, is exemplified by removal of amounts ofpolymer made per unit time, being substantially equal to the amount ofpolymer withdrawn from the reaction vessel per unit time. By“substantially equal” we intend that these amounts, polymer made perunit time, and polymer withdrawn per unit time, are in ratios of one toother, of from 0.9:1; or 0.95:1; or 0.97:1; or 1:1. In such a reactor,there will be a substantially homogeneous monomer distribution. At thesame time, the polymerization is accomplished in substantially singlestep or stage or in a single reactor, contrasted to multistage ormultiple reactors (two or more). These conditions exist forsubstantially all of the time the copolymer is produced.

Generally, without limiting in any way the scope of the invention, onemeans for carrying out a process of the present invention for theproduction of the first polymer component is as follows: (1) liquidpropylene is introduced in a stirred-tank reactor which is completely orpartly full of liquid comprising the solvent, the first polymercomponent as well as dissolved, unreacted monomer(s) as well as catalystcomponents, (2) the catalyst system is introduced via nozzles in eitherthe vapor or liquid phase, (3) feed ethylene gas, and optionally thehigher alpha olefins are introduced either into the vapor phase of thereactor, or sparged into the liquid phase as is well known in the art,(4) the reactor contains a liquid phase composed substantially ofpropylene, together with dissolved ethylene, and a vapor phasecontaining vapors of all monomers, (5) the reactor temperature andpressure may be controlled via reflux of vaporizing propylene(autorefrigeration), as well as by cooling coils, jackets, etc., (6) thepolymerization rate is controlled by the concentration of catalyst,temperature, and (7) the ethylene content of the polymer product isdetermined by the ratio of ethylene to propylene in the reactor, whichis controlled by manipulating the relative feed rates of thesecomponents to the reactor.

For example, a typical polymerization process consists of apolymerization in the presence of a catalyst comprising a chiralbis(cyclopentadienyl) metal compound and either: 1) a non-coordinatingcompatible anion activator or 2) an alumoxane activator. An exemplarycatalyst system is described in U.S. Pat. No. 5,198,401 which is hereinincorporated by reference for purposes of U.S. practices. The alumoxaneactivator is preferably utilized in an amount to provide a molaraluminum to metallocene ratio of from about 1:1 to about 20,000:1 ormore. The non-coordinating compatible anion activator is preferablyutilized in an amount to provide a molar ratio of biscyclopentadienylmetal compound to non-coordinating anion of 10:1 to about 2:3. The abovepolymerization reaction is conducted by reacting such monomers in thepresence of such catalyst system at a temperature of from about −50° C.to about 200° C. for a time of from about 1 second to about 10 hours toproduce a co(ter)polymer having a MFR between 300 g/10 min and 5000 g/10min and a PDI (polydispersity index) measured by GPC from about 1.8 toabout 4.5.

While the process of the present invention includes utilizing a catalystsystem in the liquid phase (slurry, solution, suspension or bulk phaseor combination thereof), gas phase polymerization can also be utilized.When utilized in a gas phase, slurry phase or suspension phasepolymerization, the catalyst systems will preferably be supportedcatalyst systems. See, for example, U.S. Pat. No. 5,057,475 which isincorporated herein by reference for purposes of U.S. practice. Suchcatalyst systems can also include other well-known additives such as,for example, scavengers. See, for example, U.S. Pat. No. 5,153,157 whichis incorporated herein by reference for purposes of U.S. practices.These processes may be employed without limitation of the type ofreaction vessels and the mode of conducting the polymerization. Asstated above, and while it is also true for systems utilizing asupported catalyst system, the liquid phase process comprises the stepsof contacting ethylene and propylene with the catalyst system in asuitable polymerization diluents and reacting the monomers in thepresence of the catalyst system for a time and at a temperaturesufficient to produce an ethylene-propylene copolymer of the desiredmolecular weight and composition.

According to another embodiment of the present invention, the firstpolymer component may contain small quantities of a non-conjugated dieneto aid in the vulcanization and other chemical modification of theblends. The amount of diene is preferably less than 10 wt. % andpreferably less than 5 wt. %. The diene may be selected from the groupconsisting of those which are used for the vulcanization of ethylenepropylene rubbers and are preferably ethylidene norbornene, vinylnorbornene and dicyclopentadiene. Lesser amounts of diene, typicallyless than 4 wt %, may also be used to aid in the formation of star orbranched architecture of the polymer which are expected to havebeneficial effects in the formation and the processing of the blends ofthe invention.

Catalysts and Activators for Copolymer Production Catalysts

A typical isotactic polymerization process consists of a polymerizationin the presence of a catalyst including a bis(cyclopentadienyl) metalcompound and either (1) a non-coordinating compatible anion activator,or (2) an alumoxane activator. According to one embodiment of theinvention, this process comprises the steps of contacting ethylene andpropylene with a catalyst in a suitable polymerization diluent, thecatalyst including, in one embodiment, a chiral metallocene compound,e.g., a bis(cyclopentadienyl) metal compound as described in U.S. Pat.No. 5,198,401, and an activator. U.S. Pat. No. 5,391,629 also describescatalysts useful to produce the copolymers of our invention.

The catalyst system described below useful for making the copolymers ofembodiments of our invention, is a metallocene with a non-coordinatinganion (NCA) activator, and optionally a scavenging compound.Polymerization is conducted in a solution, slurry or gas phase. Thepolymerization can be performed in a single reactor process. A slurry orsolution polymerization process can utilize sub- or superatmosphericpressures and temperatures in the range of from −25° C. to 110° C. In aslurry polymerization, a suspension of solid, particulate polymer isformed in a liquid polymerization medium to which ethylene, propylene,hydrogen and catalyst are added. In solution polymerization, the liquidmedium serves as a solvent for the polymer. The liquid employed as thepolymerization medium can be an alkane or a cycloalkane, such as butane,pentane, hexane, or cylclohexane, or an aromatic hydrocarbon, such astoluene, ethylbenzene or xylene. For slurry polymerization, liquidmonomer can also be used. The medium employed should be liquid under theconditions of the polymerization and relatively inert. Hexane or toluenecan be employed for solution polymerization. Gas phase polymerizationprocesses are described in U.S. Pat. Nos. 4,543,399; 4,588,790; and5,028,670; for example. The catalyst can be supported on any suitableparticulate material or porous carrier, such as polymeric supports orinorganic oxides, such as, for example silica, alumina or both. Methodsof supporting metallocene catalysts are described in U.S. Pat. Nos.4,808,561; 4,897,455; 4,937,301; 4,937,217; 4,912,075; 5,008,228;5,086,025; 5,147,949; and 5,238,892.

Propylene and ethylene are the monomers that can be used to make thecopolymers of embodiments of our invention, but optionally, ethylene canbe replaced or added to in such polymers with a C4 to C20 α-olefin, suchas, for example, 1-butene, 4-methyl-1-pentene, 1-hexene or 1-octene.

Metallocene

The terms “metallocene” and “metallocene catalyst precursor” are termsknown in the art to mean compounds possessing a Group 4, 5, or 6transition metal M, with a cyclopentadienyl (Cp) ligand or ligands whichmay be substituted, at least one non-cyclopentadienyl-derived ligand X,and zero or one heteroatom-containing ligand Y, the ligands beingcoordinated to M and corresponding in number to the valence thereof. Themetallocene catalyst precursors generally require activation with asuitable co-catalyst (sometimes referred to as an activator) in order toyield an active metallocene catalyst, i.e., an organometallic complexwith a vacant coordination site that can coordinate, insert, andpolymerize olefins.

Preferred metallocenes are cyclopentadienyl complexes which have two Cpring systems as ligands. The Cp ligands preferably form a bent sandwichcomplex with the metal, and are preferably locked into a rigidconfiguration through a bridging group. These cyclopentadienyl complexeshave the general formula:

(Cp¹R¹ _(m))R³ _(n)(Cp²R² _(p))MX_(q)

wherein Cp¹ and Cp² are preferably the same; R¹ and R² are each,independently, a halogen or a hydrocarbyl, halocarbyl,hydrocarbyl-substituted organometalloid or halocarbyl-substitutedorganometalloid group containing up to 20 carbon atoms; m is preferably1 to 5; p is preferably 1 to 5; preferably two R¹ and/or R² substituentson adjacent carbon atoms of the cyclopentadienyl ring associatedtherewith can be joined together to form a ring containing from 4 to 20carbon atoms; R³ is a bridging group; n is the number of atoms in thedirect chain between the two ligands and is preferably 1 to 8, mostpreferably 1 to 3; M is a transition metal having a valence of from 3 to6, preferably from group 4, 5, or 6 of the periodic table of theelements, and is preferably in its highest oxidation state; each X is anon-cyclopentadienyl ligand and is, independently, a hydrocarbyl,oxyhydrocarbyl, halocarbyl, hydrocarbyl-substituted organometalloid,oxyhydrocarbyl-substituted organometalloid or halocarbyl-substitutedorganometalloid group containing up to 20 carbon atoms; and q is equalto the valence of M minus 2.

Numerous examples of the biscyclopentadienyl metallocenes describedabove for the invention are disclosed in U.S. Pat. Nos. 5,324,800;5,198,401; 5,278,119; 5,387,568; 5,120,867; 5,017,714; 4,871,705;4,542,199; 4,752,597; 5,132,262; 5,391,629; 5,243,001; 5,278,264;5,296,434; and 5,304,614.

Illustrative, but not limiting examples of preferred biscyclopentadienylmetallocenes of the type described above are the racemic isomers of:

μ-(CH₃)₂Si(indenyl)₂M(Cl)₂,

μ-(CH₃)₂Si(indenyl)₂M(CH₃)₂,

μ-(CH₃)₂Si(tetrahydroindenyl)₂M(Cl)₂,

μ-(CH₃)₂Si(tetrahydroindenyl)₂M(CH₃)₂,

μ-(CH₃)₂Si(indenyl)₂M(CH₂CH₃)₂, and

μ-(C₆H₅)₂C(indenyl)₂M(CH₃)₂,

wherein M is Zr, Hf, or Ti.

Non-Coordinating Anions

As already mentioned, the metallocene or precursor are activated with anon-coordinating anion. The term “non-coordinating anion” means an anionwhich either does not coordinate to the transition metal cation or whichis only weakly coordinated to the cation, thereby remaining sufficientlylabile to be displaced by a neutral Lewis base. “Compatible”non-coordinating anions are those which are not degraded to neutralitywhen the initially formed complex decomposes. Further, the anion willnot transfer an anionic substituent or fragment to the cation so as tocause it to form a neutral four coordinate metallocene compound and aneutral by-product from the anion. Non-coordinating anions useful inaccordance with this invention are those which are compatible, stabilizethe metallocene cation in the sense of balancing its ionic charge, yetretain sufficient lability to permit displacement by an ethylenically oracetylenically unsaturated monomer during polymerization. Additionally,the anions useful in this invention may be large or bulky in the senseof sufficient molecular size to largely inhibit or preventneutralization of the metallocene cation by Lewis bases other than thepolymerizable monomers that may be present in the polymerizationprocess. Typically the anion will have a molecular size of greater thanor equal to 4 angstroms.

Descriptions of ionic catalysts for coordination polymerizationincluding metallocene cations activated by non-coordinating anionsappear in the early work in EP-A-0 277 003, EP-A-0 277 004, U.S. Pat.Nos. 5,198,401 and 5,278,119, and WO 92/00333. These references suggesta method of preparation wherein metallocenes (bis Cp and mono Cp) areprotonated by anionic precursors such that an alkyl/hydride group isabstracted from a transition metal to make it both cationic andcharge-balanced by the non-coordinating anion. The use of ionizing ioniccompounds not containing an active proton but capable of producing boththe active metallocene cation and a non-coordinating anion is alsoknown. See, EP-A-0 426 637, EP-A-0 573 403 and U.S. Pat. No. 5,387,568.Reactive cations other than Bronsted acids capable of ionizing themetallocene compounds include ferrocenium, triphenylcarbonium, andtriethylsilylium cations. Any metal or metalloid capable of forming acoordination complex which is resistant to degradation by water (orother Bronsted or Lewis acids) may be used or contained in the anion ofthe second activator compound. Suitable metals include, but are notlimited to, aluminum, gold, platinum and the like. Suitable metalloidsinclude, but are not limited to, boron, phosphorus, silicon and thelike.

An additional method of making the ionic catalysts uses ionizing anionicpre-cursors which are initially neutral Lewis acids but form the cationand anion upon ionizing reaction with the metallocene compounds. Forexample tris(pentafluorophenyl) boron acts to abstract an alkyl, hydrideor silyl ligand to yield a metallocene cation and stabilizingnon-coordinating anion; see EP-A-0 427 697 and EP-A-0 520 732. Ioniccatalysts for addition polymerization can also be prepared by oxidationof the metal centers of transition metal compounds by anionic precursorscontaining metallic oxidizing groups along with the anion groups; seeEP-A-0 495 375.

Illustrative, but not limiting, examples of suitable activators capableof ionic cationization of the metallocene compounds of the invention,and consequent stabilization with a resulting non-coordinating anion,include:

-   trialkyl-substituted ammonium salts such as:-   triethylammonium tetraphenylborate;-   tripropylammonium tetraphenylborate;-   tri(n-butyl)ammonium tetraphenylborate;-   trimethylammonium tetrakis(p-tolyl)borate;-   trimethylammonium tetrakis(o-tolyl)borate;-   tributylammonium tetrakis(pentafluorophenyl)borate;-   tripropylammonium tetrakis(o,p-dimethylphenyl)borate;-   tributylammonium tetrakis(m,m-dimethylphenyl)borate;-   tributylammonium tetrakis(p-trifluoromethylphenyl)borate;-   tributylammonium tetrakis(pentafluorophenyl)borate;-   tri(n-butyl)ammonium tetrakis(o-tolyl)borate and the like;-   N,N-dialkyl anilinium salts such as:-   N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate;-   N,N-dimethylanilinium tetrakis(heptafluoronaphthyl)borate;-   N,N-dimethylanilinium tetrakis(perfluoro-4-biphenyl)borate;-   N,N-dimethylanilinium tetraphenylborate;-   N,N-diethylanilinium tetraphenylborate;-   N,N-2,4,6-pentamethylanilinium tetraphenylborate and the like;-   dialkyl ammonium salts such as:-   di-(isopropyl)ammonium tetrakis(pentafluorophenyl)borate;-   dicyclohexylammonium tetraphenylborate and the like; and-   triaryl phosphonium salts such as:-   triphenylphosphonium tetraphenylborate;-   tri(methylphenyl)phosphonium tetraphenylborate;-   tri(dimethylphenyl)phosphonium tetraphenylborate and the like.

Further examples of suitable anionic precursors include those comprisinga stable carbonium ion, and a compatible non-coordinating anion. Theseinclude:

-   tropyllium tetrakis(pentafluorophenyl)borate;-   triphenylmethylium tetrakis(pentafluorophenyl)borate;-   benzene(diazonium)tetrakis(pentafluorophenyl)borate;-   tropyllium phenyltris(pentafluorophenyl)borate;-   triphenylmethylium phenyl-(trispentafluorophenyl)borate;-   benzene(diazonium)phenyl-tris(pentafluorophenyl)borate;-   tropyllium tetrakis(2,3,5,6-tetrafluorophenyl)borate;-   triphenylmethylium tetrakis(2,3,5,6-tetrafluorophenyl)borate;-   benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate;-   tropyllium tetrakis(3,4,5-trifluorophenyl)borate;-   benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate;-   tropyllium tetrakis(3,4,5-trifluorophenyl)aluminate;-   triphenylmethylium tetrakis(3,4,5-trifluorophenyl)aluminate;-   benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)aluminate;-   tropyllium tetrakis(1,2,2-trifluoroethenyl)borate;-   triphenylmethylium tetrakis(1,2,2-trifluoroethenyl)borate;-   benzene(diazonium)tetrakis(1,2,2-trifluoroethenyl)borate;-   tropyllium tetrakis(2,3,4,5-tetrafluorophenyl)borate;-   triphenylmethylium tetrakis(2,3,4,5-tetrafluorophenyl)borate;-   benzene(diazonium)tetrakis(2,3,4,5-tetrafluorophenyl)borate, and the    like.    -   A catalyst system of —(CH₃)₂Si(indenyl)₂Hf(CH₃)₂ with a        cocatalyst of N,N-dimethylanilinium        tetrakis(pentafluorophenyl)borate, can be used.

In a preferred embodiment, the activating cocatalyst, precursor ioniccompounds comprise anionic Group 13 element complexes having fourhalogenated aromatic ligands typically bulkier than substitutedtetraphenyl boron compounds of the exemplified in the identified priorart. These invention aromatic ligands consist of polycyclic aromatichydrocarbons and aromatic ring assemblies in which two or more rings (orfused ring systems) are joined directly to one another or together.These ligands, which may be the same or different, are covalently bondeddirectly to the metaumetalloid center. In a preferred embodiment thearyl groups of said halogenated tetraaryl Group 13 element anioniccomplex comprise at least one fused polycyclic aromatic hydrocarbon orpendant aromatic ring. Indenyl, napthyl, anthracyl, heptalenyl andbiphenyl ligands are exemplary. The number of fused aromatic rings isunimportant so long as the ring junctions and especially the atom chosenas the point of connection to the Group 13 element center permit anessentially tetrahedral structure. Thus, for example, suitable ligandsinclude those illustrated below, the open bond being to the Group 13atom. See also the polycyclic compound examples in the literature foradditional ligand selection, e.g., Nomenclature of Organic Compounds,Chs. 4-5 (ACS, 1974).

The choice of ligand connection point is particularly important.Substituents or ring junctions ortho to the ligand connection pointpresent such steric bulk that adoption of an essentially tetrahedralgeometry is largely precluded. Examples of undesirable connection pointsare depicted below.

Suitable mixed-ligand Group 13 complexes can include fused rings or ringassemblies with ortho-substituents, or ring junctions, so long as thoseligands do not exceed two in number. Thus Group 13 anions with one ortwo hindered fused ring aromatics with three or two unhindered ligands,where hindered aromatics are those having ortho substituents or ringjunctions (illustration II) and unhindered are those without(illustration I), will typically be suitable. Tris(perfluorophenyl)(perfluoroanthracyl)borate is an illustrative complex. In this complexthe anthracyl ligand is a hindered fused ring having ortho-substituentsbut its use with three unhindred phenyl ligands allows the complex toadopt a tetrahedral structure. Thus, generically speaking, the Group 13complexes useful in a accordance with the invention will typicallyconform to the following formula:

[M(A)_(4-n)(B)_(n)]⁺

where, M is a Group 13 element, A is an unhindered ligand as describedabove, B is a hindered ligand as described above, and n=1,2.

For both fused aromatic rings and aromatic ring assemblies, halogenationis highly preferred so as to allow for increased charge dispersion thatcontributes along with steric bulk as independent features decreasingthe likelihood of ligand abstraction by the strongly Lewis acidicmetallocene cation formed in the catalyst activation. Additionally,halogenation inhibits reaction of the hafnium cation with any remainingcarbon-hydrogen bonds of the aromatic rings, and perhalogenationprecludes such potential undesirable reactions. Thus it is preferredthat at least one third of hydrogen atoms on carbon atoms of the arylligands can be replaced by halogen atoms, and more preferred that thearyl ligands be perhalogenated. Fluorine is the most preferred halogen.

Means of preparing ionic catalyst systems comprising catalyticallyactive cations of the hafnium compounds and suitable noncoordinatinganions are conventionally known, see, for example, U.S. Pat. No.5,198,401, WO 92/00333, and WO 97/22639. Typically the methods compriseobtaining from commercial sources or synthesizing the selectedtransition metal compounds comprising an abstractable ligand, e.g.,hydride, alkyl or silyl group, and contacting them with anoncoordinating anion source or precursor compound in a suitablesolvent. The anion precursor compound abstracts a univalent hydride,alkyl or silyl ligand that completes the valency requirements of thepreferred hafnium metallocene compounds. The abstraction leaves thehafnocenes in a cationic state which is counterbalanced by the stable,compatible and bulky, noncoordinating anions according to the invention.

The noncoordinating anions are preferably introduced into the catalystpreparation step as ionic compounds having an essentially cationiccomplex which abstracts a non-cyclopentadienyl, labile ligand of thetransition metal compounds which upon abstraction of thenon-cyclopentadienyl ligand, leave as a by-product the noncoordinatinganion portion. Hafnium compounds having labile hydride, alkyl, or silylligands on the metal center are highly preferred for the ionic catalystsystems of this invention since known in situ alkylation processes mayresult in competing reactions and interactions that tend to interferewith the overall polymerization efficiency under high temperatureconditions in accordance with the preferred process embodiments of theinvention.

Suitable cations for precursor compounds capable of providing thenoncoordinating anions of the invention cocatalysts include those knownin the art. Such include the nitrogen-containing cations such as thosein U.S. Pat. No. 5,198,401, the carbenium, oxonium or sulfonium cationsof U.S. Pat. No. 5,387,568, metal cations, e.g., Ag⁺, the silyliumcations of WO 96/08519, and the hydrated salts of Group 1 or 2 metalcations of WO 97/22635. Each of the documents of this paragraph areincorporated by reference for purposes of U.S. patent practice.

Examples of preferred precursor salts of the noncoordinating anionscapable of ionic cationization of the metallocene compounds of theinvention, and consequent stabilization with a resulting noncoordinatinganion include trialkyl-substituted ammonium salts such astriethylammonium tetrakis(perfluoronapthyl) ortetrakis(perfluoro-4-biphenyl)boron, tripropylammoniumtetrakis(perfluoronapthyl) or tetrakis(perfluoro-4-biphenyl)boron,tri(n-butyl)ammonium tetrakis(perfluoronapthyl) ortetrakis(perfluoro-4-biphenyl)boron, trimethylammoniumtetrakis(perfluoronapthyl) or tetrakis(perfluoro-4-biphenyl)boron,trimethylammonium tetra tetrakis(perfluoronapthyl) ortetrakis(perfluoro-4-biphenyl)boron, tributylammoniumtetrakis(perfluoronapthyl) or tetrakis(perfluoro-4-biphenyl)boron,tripropylammonium tetrakis(perfluoronapthyl) ortetrakis(perfluoro-4-biphenyl), tributylammoniumtetrakis(perfluoronapthyl) or tetrakis(perfluoro-4-biphenyl)boron,tributylammonium tetrakis(perfluoronapthyl) ortetrakis(perfluoro-4-biphenyl)boron, tributylammoniumtetrakis(perfluoronapthyl) or tetrakis(perfluoro-4-biphenyl)boron,tri(n-butyl)ammonium tetrakis(perfluoronapthyl) ortetrakis(perfluoro-4-biphenyl)boron and the like; N,N-dialkyl aniliniumsalts such as N,N-dimethylanilinium tetrakis(perfluoronapthyl) ortetrakis(perfluoro-4-biphenyl)boron, N,N-diethylaniliniumtetrakis(perfluoronapthyl) or tetrakis(perfluoro-4-biphenyl)boron,N,N-2,4,6-pentamethylanilinium tetrakis(perfluoronapthyl) ortetrakis(perfluoro-4-biphenyl)boron and the like; dialkyl ammonium saltssuch as di-(isopropyl)ammonium tetrakis(perfluoronapthyl) ortetrakis(perfluoro-4-biphenyl)boron, dicyclohexylammoniumtetrakis(perfluoronapthyl) or tetrakis(perfluoro-4-biphenyl)boron andthe like; and triaryl phosphonium salts such as triphenylphosphoniumtetrakis(perfluoronapthyl) or tetrakis(perfluoro-4-biphenyl)boron,tri(methylphenyl)phosphonium tetrakis(per-fluoronapthyl) ortetrakis(perfluoro-4-biphenyl)boron, tri(dimethylphenyl)phosphoniumtetrakis(perfluoronapthyl) or tetrakis(perfluoro-4-biphenyl)boron andthe like.

Further examples of suitable anionic precursors include those comprisinga stable carbenium ion, and a compatible non-coordinating anion. Theseinclude tropillium tetrakis(perfluoronapthyl) ortetrakis(perfluoro-4-biphenyl) borate, triphenylmethyliumtetrakis(perfluoronapthyl) or tetrakis(perfluoro-4-biphenyl) borate,benzene (diazonium) tetrakis(perfluoronapthyl) ortetrakis(perfluoro-4-biphenyl) borate, tropilliumtetrakis(perfluoronapthyl) or tetrakis(perfluoro-4-biphenyl) borate,triphenylmethylium tetrakis(perfluoronapthyl) ortetrakis(perfluoro-4-biphenyl)borate, benzene(diazonium)tetrakis(perfluoronapthyl) or tetrakis(perfluoro-4-biphenyl)borate,tropillium tetrakis(perfluoronapthyl) or tetrakis(perfluoro-4-biphenyl)borate, triphenylmethylium tetrakis(perfluoronapthyl) ortetrakis(perfluoro-4-biphenyl)borate, benzene(diazonium)tetrakis(perfluoronapthyl) or tetrakis(perfluoro-4-biphenyl)borate. Theessentially structurally equivalent silylium borate or aluminate saltsare similarly suitable.

In yet another embodiment, the NCA portion comprises an acetylene groupand is sometimes referred to as an “acetyl-aryl” moiety. Adistinguishing feature of invention NCAs is the presence of anacetylenic functional group bound to a Group-13 atom. The Group-13 atomalso connects to at least one fluorinated ring moiety: monofluorinatedup through perfluorinated. In addition to a first ring moiety, theGroup-13 atom has two other ligands that may also be ring moietiessimilar to or different from the first ring moiety and may bemonofluorinated to perfluorinated. The goal of fluorination is to reducethe number of abstractable hydrogen. A ligand is referred to assubstantially fluorinated when enough hydrogen has beenfluorine-replaced so that the amount of remaining abstractable hydrogenis small enough that it does not interfere with commercialpolymerization.

The cationic portion of activators according to this embodimentpreferably has the form R₃PnH, wherein R represents an alkyl or arylmoiety; Pn represents a pnictide; N, P, or As; and H is hydrogen.Suitable R are shown below. This list does not limit the scope of theinvention; any R that allows the cationic portion to function asdescribed is within the scope of this invention. R includes, but is notlimited to, methyl, phenyl, ethyl, propyl, butyl, hexyl, octyl, nonyl,3-ethylnonyl, isopropyl, n-butyl, cyclohexyl, benzyl, trimethylsilyl,triethylsilyl, tri-n-propylsilyl, tri-isopropylsilyl,methylethylhexylsilyl, diethylnonlysilyl, triethylsilylpropyl,2,2-dimethyloctyl, triethylsilylethyl, tri-n-propylsilylhexyl,tri-isopropylsilyloctyl, and methyldiethylsilyloctyl.

The single sited metallocene catalysts preferred for use in the presentinvention leads to polymers which are not compositionally and tacticallyhomogeneous, both intramolecular and intermolecular, but also have alower crystallinity lower ethylene content than the catalyst systemsused hithertofore to make the polymers for the present invention. Notwanting to be limited by theory, however, believing it is worth notingthat some of the desirable properties obtained by blending the describedadditives seem likely to be derived from the following concept.

When one blends a highly isotactic polypropylene of high molecularweight with a copolymer of low molecular weight there is a tendency forthe two materials to separate partially due to the solubility differenceand partially due to the exclusion of the less crystalline copolymer.This tendency shows up as inhomogeneous separations describedillustrated by the use of TEM's and AFM's. So the highly crystallinedomains separate into islands in a sea of less crystalline or evenamorphous seas (or vice versa). In any case, what we reasoned in ourblend cases was that there would be some benefit to the properties oftensile, toughness, and softness if we could distribute some of thefirst polymer component into the high molecular weight isotactic blendpolymer which is the second polymer component. In this way some of theflexibility would be engendered to the main high molecular weight polypropylene, and some of the structure integrity of the low molecular withpolymer additive would be preserved by allowing on average higheruninterrupted defect free runs of polypropylene. An embodiment of thisinvention is to generate a soft first polymer component suitable forblending with the second polymer component which contains a lower amountof ethylene to attain a lower heat of fusion than previously known forthese low molecular weight or high MFR polymers. We note that thesefirst polymer component polymers are not atactic in the distribution ofthe methyl residues of the incorporated propylene: they are by designhighly isotactic in that a predominant amount of the propylene residuesare in the isotactic orientation. They are thus crystallizable incontact with the second polymer component. We believe that the loweramount of comonomer in the first polymer component leads to improvedredistribution of the first polymer component into the second polymercomponent due to improved miscisbility. The improved miscibility of thefirst and the second polymer component arises from a limited amount ofcomonomer in the first polymer component. It is an embodiment of thepresent invention to generate a crystallizable first polymer componentcapable of crystallizing in isotactic sequences which has neverthelesshas a low heat of fusion at low levels of the comonomer. The data forthe variation of the heat of fusion of these first polymer componentsaccording to this the preferred mode of the invention of the making thefirst polymer components is shown in FIG. 1.

Properties and Analysis of the Copolymer Elongation and Tensile Strength

Elongation and tensile strength were measured as described below. Thecopolymers of the current invention have an elongation of greater than500%, or greater than 600%, or greater than 900%.

The copolymers of the current invention have a tensile strength greaterthan 300 psi (2.1 MPa), or greater than 500 psi (3.5 MPa) or greaterthan 1000 psi (6.9 MPa).

Tensile and elongation properties are determined at 20 in/min (51cm/min) according to the procedure described in ASTM D-790. The data isreported in engineering units with no correction to the stress for thelateral contraction in the specimen due to tensile elongation. Thetensile and elongation properties of embodiments of our invention areevaluated using dumbbell-shaped samples. The samples are compressionmolded at 180° C. to 200° C. for 15 minutes at a force of 15 tons (133kN) into a plaque of dimensions of 6 in×6 in (15 cm×15 cm). The cooledplaques are removed and the specimens are removed with a die. Theelasticity evaluation of the samples is conducted on an Instron 4465,made by Instron Corporation of 100 Royall Street, Canton, Mass. Thedigital data is collected in a file collected by the Series IX MaterialTesting System available from Instron Corporation and analyzed usingExcel 5, a spreadsheet program available from Microsoft Corporation ofRedmond, Wash.

Elasticity

Embodiments of our invention are elastic after tensile deformation. Theelasticity, represented by the fractional increase in the length of thesample, represented as percent of the length of the sample, is measuredaccording to the general procedure ASTM D-790. During tensileelongation, the copolymer sample is stretched, and the polymer attemptsto recover its original dimensions when the stretching force is removed.This recovery is not complete, and the final length of the relaxedsample is slightly longer than that of the original sample. Elasticityis represented by the fractional increase in the length of the sample,expressed as a percent of the length of the original un-stretchedsample.

The protocol for measuring the elasticity of the sample consists ofprestretching the deformable zone of the dumbbell, made according to theprocedure described above for the measurement of elongation and tensilestrength, which is the narrow portion of the specimen, to 200% of itsoriginal length to prestretch the sample. This is conducted at adeformation rate of 10 inches (25 cm) per minute. The sample is relaxedat the same rate to form an analytical specimen which is a prestretchedspecimen of the original sample. This slightly oriented, orprestretched, sample is allowed to relax for 48 hours, at roomtemperature, prior to the determination of elasticity. The length of thedeformation zone in the sample is measured to be d₁. After the 48 hours,it is again deformed at 10 inches per minute for a 200% extension of thedeformation zone of the sample and allowed to relax at the same rate.The sample is removed and after 10 minutes of relaxation the sample ismeasured to have a new length of the deformation zone of d₂. Theelasticity of the sample as a percent is determined as 100*(d₂−d₁)/d₁.

Embodiments of the invention have elasticity, as measured by theprocedure described above, of less than 30%, or less than 20%, or lessthan 10%, or less than 8% or less than 5%.

These values of the elasticity over the range of composition of thecopolymer vary with the tensile strength of the sample as measured bythe 500% tensile modulus. Elasticity of this family of copolymers isthus represented by two criteria: (a) extensibility to 500% elongationwith a measurable modulus (500% tensile modulus) and (b) elasticity froman extension to 200% elongation on a slightly oriented sample asdescribed above. First, the copolymer of embodiments of our inventionshould have a measurable tensile strength at 500% elongation (also knownas 500% tensile modulus), of greater than 0.5 MPa, or greater than 0.75MPa, or greater than 1.0 MPa, or greater than 2.0 MPa; and second, thecopolymer should have the above-described elasticity.

Alternatively, the relationship of elasticity to 500% tensile modulusmay be described. Referring to FIG. 3, elasticity is plotted versus 500%tensile modulus in MPa for copolymers of the invention. The plotted datacorrespond to Samples 5-14 in Table 6 of the Examples herein. A linearregression fit of the data yields a relationship of:

Elasticity(%)=0.9348M−1.0625

where M is the 500% tensile modulus in MPa. In embodiments of thepresent invention, the elasticity as a function of 500% tensile modulusin MPa is defined by:

Elasticity(%)≦0.935M+12; or

Elasticity(%)≦0.935M+6; or

Elasticity(%)≦0.935M.

Flexural Modulus

Softness of the copolymers of embodiments of the invention may bemeasured by flexural modulus. Flexural modulus is measured in accordancewith ASTM D790, using a Type IV dogbone at crosshead speed of 0.05in/min (1.3 mm/min). The values of the flexural modulus over the rangeof composition of the copolymer vary with the tensile strength of thesample as measured by the 500% tensile modulus. Flexural modulus of thisfamily of copolymers is thus represented by two criteria: (a)extensibility to 500% elongation with a measurable modulus (500% tensilemodulus); and (b) flexural modulus.

A single exponential fit of the data yields a relationship of:

Flexural Modulus(MPa)=4.1864e ^(0.269M)

where M is the 500% tensile modulus in MPa. In embodiments of thepresent invention, the flexural modulus in MPa as a function of 500%tensile modulus in MPa is defined by:

Flexural Modulus≦4.2e ^(0.27) M+50; or

Flexural Modulus≦4.2e ^(0.27) M+30; or

Flexural Modulus≦4.2e ^(0.27) M+10; or

Flexural Modulus≦4.2e ^(0.27) M+2.

the copolymer contains less than 10000 ppm or less than 5000 ppm or lessthan 3000 ppm, less than 2000 ppm or less than 1000 ppm or less than 500ppm or less than 250 ppm of a molecular degradation agent or its reactorproducts for propylene dominated polymers.

Second Polymer Component

The second polymer component, the polypropylene component, is acopolymers of propylene, a mixture of copolymers, or a combination ofhomopolymers and copolymers. The second polymer component may alsocontain additives such as flow improvers, nucleators and antioxidantswhich are normally added to isotactic polypropylene to improve or retainproperties.

-   (i) In one embodiment, the polypropylene of the present invention is    predominately crystalline, i.e., it has a melting point generally    greater than about 110° C., preferably greater than about 115° C.,    and most preferably greater than about 130° C. Preferably, it has a    heat of fusion greater than 75 J/g.-   (ii) In a further embodiment, the polypropylene can vary widely in    composition. For example, the propylene copolymer containing equal    to or less than about 10 weight percent of other monomer, i.e., at    least about 90% by weight propylene can be used. Further, the    polypropylene can be present in the form of a graft or block    copolymer, in which the blocks of polypropylene have substantially    the same stereo regularity as the propylene-ethylene copolymer, so    long as the graft or block copolymer has a melting point above about    110° C., preferably above 115° C., and more preferably above 130°    C., characteristic of the stereo regular propylene sequences. The    propylene polymer component may be a combination of    homopolypropylene, and/or random, and/or block copolymers as    described herein. When the above propylene polymer component is a    random copolymer, the percentage of the copolymerized alpha-olefin    in the copolymer is, in general, from about 0.5% to about 9% by    weight, preferably about 2% to about 8% by weight, most preferably    about 2% to about 6% by weight. The preferred alpha-olefins contain    2 or from 4 to about 12 carbon atoms. The most preferred    alpha-olefin is ethylene. One or two or more alpha-olefins can be    copolymerized with propylene.

Exemplary alpha-olefins may be selected from the group consisting ofethylene; butene-1; pentene-1,2-methylpentene-1,3-methylbutene-1;hexene-1,3-methylpentene-1,4-methylpentene-1,3,3-dimethylbutene-1;heptane-1; hexene-1,3-methylhexene-1; dimethylpentene-1trimethylbutene-1; ethylpentene-1; octene-1; methylpentene-1;dimethylhexene-1; trimethylpentene-1; ethylhexene-1;methylethylpentene-1; diethylbutene-1; propylpentane-1; decene-1;methylnonene-1; nonene-1; dimethyloctene-1; trimethylheptene-1;ethyloctene-1; methylethylbutene-1; diethylhexene-1; dodecene-1 andhexadodecene-1.

-   (iii) In a further embodiment, t is understood that in the context    of the any or all of the above embodiments the MFR of the second    polymer component is less than 200 g/10 min, less than 150 g/10 min,    less than 100 g/10 min, less than 75 g/10 min. less than 50 g/10    min, less than 30 g/10 min, less than 20 g/10 min or preferably less    than 10v or less than 5 g/10 min or less than 3 g/10 min or less    than 2 g/10 min. Blends as described in the embodiments can be made    with any of the MFR ranges described above, however those made with    the greater MFR of the second polymer component invariably tend to    have a lower value of the Z parameter described herein-   (iv) In a further embodiment, the inventive blend compositions may    comprise from about 1% to about 95% by weight of the second polymer    component. According to a preferred embodiment, the thermoplastic    polymer blend composition of the present invention may comprise from    about 20% to about 70% by weight of the second polymer component.    According to the most preferred embodiment, the compositions of the    present invention may comprise from about 25% to about 60% by weight    of the second polymer component.

There is no particular limitation on the method for preparing thispropylene polymer component of the invention. However, in general,copolymers may be obtained by copolymerizing propylene and analpha-olefin having 2 or from 4 to about 20 carbon atoms, preferablyethylene, in a single stage or multiple stage reactor. Polymerizationmethods include high pressure, slurry, gas, bulk, or solution phase, ora combination thereof, using a traditional Ziegler-Natta catalyst or asingle-site, metallocene catalyst system. The catalyst used ispreferably one which has a high isospecificity. Polymerization may becarried out by a continuous or batch process and may include use ofchain transfer agents, scavengers, or other such additives as deemedapplicable.

It is preferred for the purpose of the invention to choose the secondpolymer component such that it has the lowest possible flexural modulus[value] while still having a melting point above the designatedspecification. In this regard a random copolymer of propylene andanother olefin such as ethylene such as Escorene PP 9302, available fromthe ExxonMobil Chemical Co. of Houston, Tex. will be considered as apreferred embodiment.

The mechanism by which the desirable characteristics of the presentcopolymer blends are obtained is not fully understood. However, it isbelieved to involve a co-crystallization phenomenon between propylenesequences of similar stereoregularity in the various polymericcomponents, which results in a narrowing of the differences in thecrystallization temperature of the blend components. The combinedcomponents have a blend melting point closer together than would beexpected on a comparison of the properties of the individual componentsalone. Surprisingly, some blend compositions have a singlecrystallization temperature and a single melting temperature, since itwould be expected by those skilled in the art that the blending of twocrystalline polymers would result in a double crystallizationtemperature as well as a double melting temperature reflecting the twopolymeric components. However, the intimate blending of the polymershaving the required crystallinity characteristics apparently results ina crystallization phenomenon that modifies the other physical propertiesof the propylene/ethylene copolymer, thus measurably increasing itscommercial utility and range of applications.

While the above discussion has been limited to the description of theinvention in relation to having only components one and two, as will beevident to those skilled in the art, the polymer blend compositions ofthe present invention may comprise other additives. Various additivesmay be present to enhance a specific property or may be present as aresult of processing of the individual components. Additives which maybe incorporated include, for example, fire retardants, antioxidants,plasticizers, pigments, vulcanizing or curative agents, vulcanizing orcurative accelerators, cure retarders, processing aids, flameretardants, tackifying resins, and the like. These compounds may includefillers and/or reinforcing materials. These include carbon black, clay,talc, calcium carbonate, mica, silica, silicate, combinations thereof,and the like. Other additives which may be employed to enhanceproperties include antiblocking agents, coloring agent. Lubricants, moldrelease agents, nucleating agents, reinforcements, and fillers(including granular, fibrous, or powder-like) may also be employed.Nucleating agents and fillers tend to improve rigidity of the article.The list described herein is not intended to be inclusive of all typesof additives which may be employed with the present invention. Uponreading this disclosure, those of skill in the art will appreciate otheradditives may be employed to enhance properties of the composition. Asis understood by the skilled in the art, the polymer blend compositionsof the present invention may be modified to adjust the characteristicsof the blend as desired.

The blends of the present invention may be prepared by any procedurethat guarantees an intimate mixture of the components. For example, thecomponents can be combined by melt pressing the components together on aCarver press to a thickness of about 0.5 millimeter (20 mils) and atemperature of about 180° C., rolling up the resulting slab, folding theends together, and repeating the pressing, rolling, and foldingoperation about 10 times. Internal mixers are particularly useful forsolution or melt blending. Blending at a temperature of about 180° C. to240° C. in a Brabender Plastograph for about 1 to 20 minutes has beenfound satisfactory. Still another method that may be used for admixingthe components involves blending the polymers in a Banbury internalmixer above the flux temperature of all of the components, e.g., 180° C.for about 5 minutes. A complete mixture of the polymeric components isindicated by the uniformity of the morphology of the dispersion of thecomponents of the mixture. Continuous mixing may also be used. Theseprocesses are well known in the art and include single and twin screwmixing extruders, static mixers for mixing molten polymer streams of lowviscosity, impingement mixers, as well as other machines and processes,designed to disperse the first polymer component and the second polymercomponent in intimate contact. The polymer blends of the instantinvention exhibit a remarkable combination of desirable physicalproperties. The incorporation of as little as 5% the second polymercomponent in the other components increases the melting point of theblend. In addition, the incorporation of the second polymer component inaccordance with the instant invention may nearly eliminates thestickiness characteristic of the propylene/ethylene copolymer alone.

Blends of the First Polymer Component, Second Polymer Component, and thePlasticizer

In a further embodiment, a plasticizer can be optimally added to the allof the polymer blend compositions of the present invention.

In one embodiment the plasticizer is process oil. The addition ofprocess oil in moderate amounts lowers the viscosity and flexibility ofthe blend while improving the properties of the blend at temperaturesnear and below 0 C. It is believed that these benefits arise by thelowering of the T_(g) of the blend comprising the mixture of the firstpolymer component and second polymer component. Additional benefits ofadding plasticizer to blends of the first polymer component and secondpolymer component the include improved processibility and a betterbalance of elastic and tensile strength are anticipated.

The process oil is typically known as extender oil in the rubberapplication practice. The process oils can consist of (a) hydrocarbonsconsisting of essentially of carbon and hydrogen with traces ofheteroatom such as oxygen or (b) essentially of carbon, hydrogen and atleast one heteroatom such as dactyl phthalate, ethers and polyether. Theprocess oils have a boiling point to be substantially involatile at 200°C. These process oils are commonly available either as neat solids orliquids or as physically absorbed mixtures of these materials on aninert support (e.g., clays, silica) to form a free flowing powder.

The process oils usually include a mixture of a large number of chemicalcompounds which may consist of linear, acyclic but branched, cyclic andaromatic carbonaceous structures. Another family of process oils arecertain low to medium molecular weight (Molecular weight (Mn)<110,000)organic esters and alkyl ether esters. Examples of process oils areSunpar® 150 and 220 from The Sun Manufacturing Company of Marcus Hook,Pa., USA and Hyprene® V750 and Hyprene V1200 from Ergon, Post Office Box1639, Jackson, Miss. 39215-1639, USA. and IRM 903 from CalumetLubricants Co., 10234 Highway 157, Princeton, La. 71067-9172, USA. It isalso anticipated that combinations of process oils each of which isdescribed above may be used in the practice of the invention. It isimportant that in the selection of the process oil be compatible ormiscible with the polymer blend composition of the present invention inthe melt to form a homogenous one phase blend.

The addition of the process oils to the mixture comprising the firstpolymer component and the second polymer component maybe made by any ofthe conventional means known to the art. These include the addition ofall or part of the process oil prior to recovery of the polymer as wellas addition of the process oil, in whole or in part, to the polymer as apart of a compounding for the interblending of the first polymercomponent and the second polymer component. The compounding step may becarried out in a batch mixer such as a mill or an internal mixer such asBanbury mixer. The compounding operation may also be conducted in acontinuous process such as a twin screw extruder.

The addition of certain process oils to lower the glass transitiontemperature of blends of isotactic polypropylene and ethylene propylenediene rubber has been described in the art by Ellul in U.S. Pat. Nos.5,290,886 and 5,397,832. These procedures are easily applicable to thecurrent invention.

In a further embodiment the plasticizer is a synthetic alkane lubricant.The synthetic lubricant of the present invention is a compoundcomprising carbon and hydrogen, and does not include to an appreciableextent functional groups selected from hydroxide, aryls and substitutedaryls, halogens, alkoxys, carboxylates, esters, carbon unsaturation,acrylates, oxygen, nitrogen, and carboxyl. By “appreciable extent”, itis meant that these groups and compounds comprising these groups are notdeliberately added, and if present at all, is present at less than 5 wt% by weight in one embodiment. In one embodiment, it comprises C₆ toC₂₀₀ paraffins, and C₈ to C₁₀₀ paraffins in another embodiment. Inanother embodiment, it consists essentially of C₆ to C₂₀₀ paraffins, andconsists essentially of C₈ to C₁₀₀ paraffins in another embodiment. Forpurposes of the present invention and description herein, the term“paraffin” includes all isomers such as n-paraffins, branched paraffins,isoparaffins, and may include cyclic aliphatic species, and blendsthereof, and may be derived synthetically by means known in the art, orfrom refined crude oil in such a way as to meet the requirementsdescribed herein. It will be realized that the classes of materialsdescribed herein that are useful can be utilized alone or admixed inorder to obtain desired properties.

This invention further relates to plasticized polyolefin compositionscomprising one or more polyolefins and one or more non-functionalizedplasticizers where the non-functionalized plasticizer has a kinematicviscosity (“KV”) of 2 cSt or less at 100° C., preferably 1.5 cSt orless, preferably 1.0 cSt or less, preferably 0.5 cSt or less (asmeasured by ASTM D 445). In another embodiment the plasticizer having aKV of 2 cSt or less at 100° C. also has a glass transition temperature(Tg) that cannot be determined by ASTM E-1356 or if it can be determinedthen the Tg according to ASTM E-1356 is less than 30° C. preferably lessthan 20° C., more preferably less than 10° C., more preferably less than0° C., more preferably less than −5° C., more preferably less than −10°C., more preferably less than −15° C.

Suitable isoparaffins are commercially available under the tradenameISOPAR (ExxonMobil Chemical Company, Houston Tex.), and are describedin, for example, U.S. Pat. Nos. 6,197,285; 3,818,105; and 3,439,088, andsold commercially as ISOPAR series of isoparaffins, some of which arecalled ISOPAR E, ISOPAR G, ISOPAR H, ISOPAR K, ISOPAR L, ISOPAR M andISOPAR V.

Other suitable isoparaffins are also commercial available under thetrade names SHELLSOL (by Shell), SOLTROL (by Chevron Phillips) and SASOL(by Sasol Limited). SHELLSOL is a product of the Royal Dutch/Shell Groupof Companies). SOLTROL is a product of Chevron Phillips Chemical Co. LP,for example, SOLTROL 220 (boiling point=233-280° C.). SASOL is a productof Sasol Limited (Johannesburg, South Africa), for example, SASOLLPA-210, SASOL-47 (boiling point=238-274° C.).

Suitable n-paraffins are commercially available under the tradenameNORPAR (ExxonMobil Chemical Company, Houston, Tex.), and are soldcommercially as NORPAR series of n-paraffins, some of which aresummarized in Table below.

Suitable dearomatized aliphatic hydrocarbons are commercially availableunder the tradename EXXSOL (ExxonMobil Chemical Company, Houston, Tex.),and are sold commercially as EXXSOL series of dearomaticized aliphatichydrocarbons,

In a further embodiment, the plasticizer is polyalpha olefin includingatactic polypropylene. The polyalpha olefins (PAO) comprises oligomersof linear olefins having 3 to 14 carbon atoms, more preferably 8 to 12carbon atoms, more preferably 10 carbon atoms having a Kinematicviscosity of 10 or more (as measured by ASTM D-445); and preferablyhaving a viscosity index (“VI”), as determined by ASTM D-2270 of 100 ormore, preferably 110 or more, more preferably 120 or more, morepreferably 130 or more, more preferably 140 or more; and/or having apour point of −5° C. or less (as determined by ASTM D-97), morepreferably −10° C. or less, more preferably −20° C. or less. PreferredPAO's are described more particularly in, for example, U.S. Pat. Nos.5,171,908 and 5,783,531 and in SYNTHETIC LUBRICANTS AND HIGH PERFORMANCEFUNCTIONAL FLUIDS 1-52 (Leslie R. Rudnick & Ronald L. Shubkin, ed.Marcel Dekker, Inc. 1999). PAO's useful in the present inventiontypically possess a number average molecular weight of from 100 to21,000 in one embodiment, and from 200 to 10,000 in another embodiment,and from 200 to 7,000 in yet another embodiment, and from 200 to 2,000in yet another embodiment, and from 200 to 500 in yet anotherembodiment. Preferred PAO's have viscosities in the range of 0.1 to 150cSt at 100° C., and from 0.1 to 3000 cSt at 100° C. in anotherembodiment (ASTM D-445). PAO's useful in the present invention typicallyhave pour points of less than 0° C. in one embodiment, less than −10° C.in another embodiment, and less than −20° C. in yet another embodiment,and less than −40° C. in yet another embodiment. Desirable PAO's arecommercially available as SHF and SuperSyn PAO's (ExxonMobil ChemicalCompany, Houston Tex.), some of which are SHF-200, SHF-210, SHF-230,SHF-410, SHF-61/630, SHF-82/830, SHF-1010, SHF-403, SHF-100, SuperSyn215, SuperSyn 230, SuperSyn 210, SuperSyn 230.

Other useful PAO's include those sold under the tradenames Synfluid®available from ChevronPhillips Chemical Co. in Pasedena Tex., Durasyn®available from BP Amoco Chemicals in London England, Nexbase® availablefrom Fortum Oil and Gas in Finland, Synton® available from CromptonCorporation in Middlebury Conn., USA, EMERY® available from CognisCorporation in Ohio, USA.

Commercial examples of useful polybutenes include the PARAPOL® Series ofprocessing oils (Infineum, Linden, N.J.), such as PARAPOL® 450, 700,950, 1300, 2400 and 2500 and the Infineum “C” series of polybutenes,including C9945, C9900, C9907, C9913, C9922, C9925 as listed below. Thecommercially available PARAPOL® and Infineum Series of polybuteneprocessing oils are synthetic liquid polybutenes, each individualformulation having a certain molecular weight, all formulations of whichcan be used in the composition of the invention. The molecular weightsof the PARAPOL® oils are from 420 Mn (PARAPOL® 450) to 2700 Mn (PARAPOL®2500) as determined by gel permeation chromatography. The MWD of thePARAPOL® oils range from 1.8 to 3 in one embodiment, and from 2 to 2.8in another embodiment; the pour points of these polybutenes are lessthan 25° C. in one embodiment, less than 0° C. in another embodiment,and less than −10° C. in yet another embodiment, and between −80° C. and25° C. in yet another embodiment; and densities (IP 190/86 at 20° C.)range from 0.79 to 0.92 g/cm³, and from 0.81 to 0.90 g/cm³ in anotherembodiment.

In another embodiment the plasticizer may be a high T_(g) plasticizer.The use of a high T_(g) plasticizer has a distinct effect on theproperties of the blend in response to changes in temperature in such away that it may be possible at room temperature to have blends whichhave a characteristic leathery feel in contrast to the formation ofblends which have a rubbery feel when low T_(g) components are used asplasticizers.

The plasticizers of this embodiment of the present invention areselected to be miscible with the polymer. The resins are miscible ifthey meet the following criteria. In a differential scanning calorimetry(DSC) experiment, a polymer composition including the polymer and othercomponents such as process oil show a single glass transitiontemperature (T_(g) 1) between 20° C. and −50° C.; a correspondingpolymer blend containing the polymer composition with the hydrocarbonresin added also show a single glass transition temperature (T_(g) 2);and T_(g) 2 is higher than T_(g) 1 by at least 1° C. The resins of thepresent invention preferably have a glass transition temperature, byDSC, of greater than 20° C.

Resins used in embodiments of the present invention have a softeningpoint within the range having an upper limit of 180° C., 150° C., or140° C., and a lower limit of 80° C., 120° C., or 125° C. Softeningpoint (° C.) is measured as a ring and ball softening point according toASTM E-28 (Revision 1996).

The resin is present in the inventive blend compositions in an amountranging from a lower limit of 1%, 5%, or 10% by weight based on thetotal weight of the composition, to an upper limit of 30%, or 25%, or20%, or 18%, or 15% by weight based on the total weight of thecomposition.

Various types of natural and synthetic resins, alone or in admixturewith each other, can be used in preparing the compositions describedherein, provided they meet the miscibility criteria described herein.Suitable resins include, but are not limited to, natural rosins androsin esters, hydrogenated rosins and hydrogenated rosin esters,coumarone-indene resins, petroleum resins, polyterpene resins, andterpene-phenolic resins. Specific examples of suitable petroleum resinsinclude, but are not limited to aliphatic hydrocarbon resins,hydrogenated aliphatic hydrocarbon resins, mixed aliphatic and aromatichydrocarbon resins, hydrogenated mixed aliphatic and aromatichydrocarbon resins, cycloaliphatic hydrocarbon resins, hydrogenatedcycloaliphatic resins, mixed cycloaliphatic and aromatic hydrocarbonresins, hydrogenated mixed cycloaliphatic and aromatic hydrocarbonresins, aromatic hydrocarbon resins, substituted aromatic hydrocarbons,and hydrogenated aromatic hydrocarbon resins. As used herein,“hydrogenated” includes fully, substantially and at least partiallyhydrogenated resins. Suitable aromatic resins include aromatic modifiedaliphatic resins, aromatic modified cycloaliphatic resin, andhydrogenated aromatic hydrocarbon resins. Any of the above resins may begrafted with an unsaturated ester or anhydride to provide enhancedproperties to the resin. Examples of grafted resins and theirmanufacture are described in PCT Applications PCT/EP02/10794,PCT/EP02/10795, PCT/EP02/10796, and PCT/EP02/10686, which are fullyincorporated herein by reference for U.S. purposes. For additionaldescription of resins, reference can be made to technical literature,e.g., Hydrocarbon Resins, Kirk-Othmer, Encyclopedia of ChemicalTechnology, 4th Ed. Vol. 13, pp. 717-743 (J. Wiley & Sons, 1995).

Hydrogenated petroleum resins are usually prepared by catalyticallyhydrogenating a thermally polymerized steam cracked petroleum distillatefraction, especially a fraction having a boiling point of between 20° C.and 280° C. These fractions usually are of compounds having one or moreunsaturated cyclic rings in the molecule, such as cyclodienes,cycloalkenes, and indenes. It is also possible to hydrogenate resinsproduced by the catalytic polymerization of unsaturated hydrocarbons.Before hydrogenation occurs the polymerized resin is usually dissolvedin a saturated hydrocarbon solvent such as heptane. The hydrogenationcatalysts that may be used include nickel, reduced nickel, or molybdenumsulphide. Hydrogenation can take place in a single stage at atemperature of 200° C. to 330° C., at a pressure of 20. 26 to 121.56 bar(20 to 120 atmospheres) for a period of 5 to 7 hours. After filteringoff the catalyst, the solvent is removed by distillation and recoveredfor recycling. An improved hydrogenation process leading to increasedyields of high quality hydrogenated hydrocarbon resins is described inEP 0 082 726.

Resins suited for use as described herein include EMPR 100, 101, 102,103, 104, 105, 106, 107, 108, 109, 110, 116, 117, and 118 resins,OPPERA® resins, and EMFR resins available from ExxonMobil ChemicalCompany, ARKON® P140, P125, P115, M115, and M135 and SUPER ESTER® rosinesters available from Arakawa Chemical Company of Japan, SYLVARES®polyterpene resins, styrenated terpene resins and terpene phenolicresins available from Arizona Chemical Company, SYLVATAC® and SYLVALITE®rosin esters available from Arizona Chemical Company, NORSOLENE®aliphatic aromatic resins available from Cray Valley of France,DERTOPHENE® terpene phenolic resins and DERCOLYTE® polyterpene resinsavailable from DRT Chemical Company of France, EASTOTAC® resins,PICCOTAC® resins, REGALITE® and REGALREZ® hydrogenatedcycloaliphatic/aromatic resins available from Eastman Chemical Companyof Kingsport, Tenn., WINGTACK® resins available from Goodyear ChemicalCompany, PICCOLYTE® and PERMALYN® polyterpene resins, rosins and rosinesters available from Hercules (now Eastman Chemical Company),coumerone/indene resins available from Neville Chemical Company,QUINTONE® acid modified C₅ resins, C₅/C₉ resins, and acid modified C₅/C₉resins available from Nippon Zeon of Japan, CLEARON® hydrogenatedterpene resins available from Yasuhara. The preceding examples areillustrative only and by no means limiting.

In one embodiment, the hydrocarbon resin has a number average molecularweight (Mn) within the range having an upper limit of 5000, or 2000, or1000, and a lower limit of 200, or 400, or 500, a weight averagemolecular weight (Mw) ranging from 500 to 5000, a Z average molecularweight (Mz) ranging from 500 to 10,000, and a polydispersity (PD) asmeasured by Mw/Mn of from 1.5 to 3.5, where Mn, Mw, and Mz aredetermined by size exclusion chromatography (SEC). In anotherembodiment, the hydrocarbon resin has a lower molecular weight than thepolymer.

The blends including the plasticizer and other components may beprepared by any procedure that guarantees an intimate mixture of thecomponents. For example, the components can be combined by melt pressingthe components together on a Carver press to a thickness of about 0.5millimeter (20 mils) and a temperature of about 180° C., rolling up theresulting slab, folding the ends together, and repeating the pressing,rolling, and folding operation about 10 times. Internal mixers areparticularly useful for solution or melt blending. Blending at atemperature of about 180° C. to 240° C. in a Brabender Plastograph forabout 1 to 20 minutes has been found satisfactory. Still another methodthat may be used for admixing the components involves blending thepolymers in a Banbury internal mixer above the flux temperature of allof the components, e.g., 180° C. for about 5 minutes. A complete mixtureof the polymeric components is indicated by the uniformity of themorphology of the dispersion of the components of the mixture.Continuous mixing may also be used. These processes are well known inthe art and include single and twin screw mixing extruders, staticmixers for mixing molten polymer streams of low viscosity, impingementmixers, as well as other machines and processes, designed to dispersethe first polymer component and the second polymer component in intimatecontact. The polymer blends of the instant invention exhibit aremarkable combination of desirable physical properties. Theincorporation of as little as 5% the second polymer component in theother components increases the melting point of the blend. In addition,the incorporation of the second polymer component in accordance with theinstant invention may nearly eliminates the stickiness characteristic ofthe propylene/ethylene copolymer alone.

One preferable embodiment is blending the first polymer component with apeak melting point by DSC less than 105° C. having about 4 wt. % toabout 35 wt. % ethylene (wt. % of the first polymer component) andhaving a heat of fusion of less than 15 J/g, with the second polymercomponent having about 0.5% to about 9% ethylene (wt. % of the secondpolymer component) and a MFR less than 15 g/10 min. Both the first andsecond polymer components may have isotactic propylene sequences longenough to crystallize. These blends may also include a process oil wherethe process oil is present in less than 20 weight percent of the blend.

A preferred blend of the above two embodiments comprises 25 to 35 wt %of the first polymer component and 30 to 50 wt % of the second polymercomponent and the balance being process oil.

According to another preferred embodiment the thermoplastic polymerblend, the second polymer component as described above is selected froman isotactic polypropylene, a reactor copolymer or an impact copolymerand is present in an amount of about 1% to about 95% by weight and morepreferably 2% to 70% by weight of the total weight of the blend.

According to still a further preferred embodiment, the invention isdirected to a process for preparing thermoplastic polymer blendcompositions. The process comprises: (a) polymerizing a mixture ofethylene and propylene in the presence of a chiral metallocene catalyst,wherein a copolymer of propylene and the ethylene is obtained comprisinggreater than about 65% by weight propylene and greater than 80% byweight propylene and containing isotactically crystallizable propylenesequences and having an MFR greater than 500 g/10 min; (b) polymerizinga mixture of propylene and one or more monomers selected from ethyleneor C 3-C 20 α-olefins in the presence of a polymerization catalystwherein a substantially isotactic propylene polymer containing about 91%to about 99.5% by weight polymerized propylene with a melting point byDSC greater than 100° C. and an MFR less than 50 g/10 min; and (c)blending the propylene polymer of step (a) with the copolymer of step(b) to form a blend in the presence of optional amounts of plasticizer.

According to yet another preferred embodiment the plasticizer is anamorphous polymer of propylene or a copolymer of propylene and anotheralpha olefin and is formed concurrently with the first polymer componentby the addition of second catalysts to that polymerization process whichallows the production of an atactic and amorphous copolymer.

The invention is directed to the formation of a blend of the componentsA and B, with optional amounts of C which has a phase morphologyconsisting of domains of different crystallinities. These domains arevery small. The domains of the dispersed phase are small with an averagemaximum axis less than 5 μm.

The benefits of the invention are the formation of compositions whichare simultaneously tough and yet are flexible and easily fabricated.This is shown by reference to the diagram in FIG. 1. In noninventivecompositions crystallinity, fluidity and molecular weight (representedby Mz) have orthogonal effects on the properties of the composition. Inthis invention the selection of the molecular weights and thecrystallinities of the components lead to materials which have theseseemingly contradictory combinations of properties.

Inorganic Fillers

The embodiments of the instant invention can contain inorganicparticulate fillers. The inorganic particulate fillers are used toimprove the mechanical and wear properties of the compound of theinstant invention. Typically less than 40 wt %, more preferably lessthan 30 wt % of the inorganic filler is used in these formulations. Theparticulate fillers include particles less than 1 mm in diameter, rodless than 1 cm in length and plates less than 0.2 sq. cm. in surfacearea. Exemplary particulate fillers include carbon black, clays,titanium and magnesium oxides and silica. In addition, other particulatefillers such as calcium carbonate, zinc oxide, whiting, magnesium oxidecan also be used. Examples of rod like filler are glass fibers. Examplesof plate like fillers are mica. The addition of very small particulatefillers, commonly referred to as nanocomposites, is also contemplated inthis invention.

In a preferred embodiment, the blend composition according to thisinvention is formed contains 1% by weight or more of particulate filler,more preferably 2% by weight or more, even more preferably 3% by weightor more, most preferably 4% by weight or more.

Typically, the composition of this invention contains 40% by weight orless of particulate filler, more preferably 35% by weight or less, evenmore preferably 30% by weight or less, most preferably 25% by weight orless.

The addition of the fillers does change the properties of the compoundof the instant invention. In particular, compounds with the inorganicfiller have improved thermal stability and resistance to wear. Inaddition the addition of white fillers improve the temperature changesof the hydrocarbon polymers on exposure to sunlight. However theaddition of fillers, beyond a certain level, does lead to a dramaticincrease in the viscosity and a corresponding decrease in theprocessability. This threshold level is the percolation threshold. Inaddition to the m increase in the viscosity the percolation threshold isalso accompanied by an improvement in the elastic properties and atslightly higher levels of the filler above the percolation threshold adrop in the elastic recovery of the blend. The percolation threshold isattained at different levels of addition of fillers depending on thetype of filler used. With in any one family of filler (e.g., carbonblack) the percolation threshold is attained at lower levels than forthe fillers with a smaller size than for the fillers with a larger size.It is important for the compounding of the blends of the instantinvention to reach a filler level which is slightly lower than thepercolation threshold such that while the beneficial properties of thefillers addition are retained the effect of addition of filler beyondthe percolation threshold on the processability and the elasticity ofthe blend are avoided. In this embodiment of the invention we show inexamples the data for the percolation threshold and the rise inviscosity for a variety of commonly used fillers.

Hitherto fore the creation of a hydrocarbon polymeric composition whichhas easily moldable and soft while simultaneously having high tensile,elongation and tear strength and good moldability have been difficult.Ease of moldability depends on the low viscosity, high crystallizationtemperature and a high rate of crystallization. Tensile strength dependson the presence of a large amount of crystalline material which canimpart strength and toughness to the composition. Softness depends onlow level of crystallinity and the presence of a predominant fraction ofamorphous material. A high level of elongation and tear strengthsimilarity depends on the existence of a large amount of a highmolecular weight but amorphous material. In the Table below, thephysical properties (which have been indicated above) that representsome of the different embodiments of the present invention are shown.

TABLE 2 Ranges and vales of properties of inventive compositionsProperty Procedure/units Preferable More preferable Most preferableFluidity Melt Flow rate in dg/min Greater than 20 Greater than 50Greater than 80 Softness Flexural Modulus (1% secant) in kpsi Less than50 Less than 30 Less than 20 Toughness Tensile strength in psi Greaterthan 800 Greater than 1200 Greater than 1500 Tear Resistance Die C tearin lbf/in Greater than 150 Greater than 250 Greater than 300Extensibility Elongation in % Greater than 350 Greater than 650 Greaterthan 800 Crystallization Crystallization T in C. Greater than 65 Greaterthan 75 Greater than 85 Surface stickiness Finger touch Not detected Notdetected Not detected

The selection of a low molecular weight crystallizable polypropylene anda high molecular weight substantially isotactic PP as leads to blendcompositions which have a combination of enhanced moldability, enhancedtensile strength as well as being soft and with exceptional amount oftensile elongation and tear strength. In a preferred embodiment of thisselection, the addition of process oil to the above blend leads tosoftening of the polymer composition and enhanced fluidity while havingonly small effects on the properties such as tensile and tear.

Fabrication

The blends of the instant invention may be fabricated into injectionmolded objects, sheets, cast and blown films and roto moleded or slushmolded articles by processes well known in the art.

Certain embodiments and features have been described using a set ofnumerical upper limits and a set of numerical lower limits. It should beappreciated that ranges from any lower limit to any upper limit arecontemplated unless otherwise indicated. Certain lower limits, upperlimits and ranges appear in one or more claims below. All numericalvalues are “about” or “approximately” the indicated value, and take intoaccount experimental error and variations that would be expected by aperson having ordinary skill in the art.

Various terms have been defined above. To the extent a term used in aclaim is not defined above, it should be given the broadest definitionpersons in the pertinent art have given that term as reflected in atleast one printed publication or issued patent. Furthermore, allpatents, test procedures, and other documents, including prioritydocuments, cited in this application are fully incorporated by referenceto the extent such disclosure is not inconsistent with this applicationand for all jurisdictions in which such incorporation is permitted.

While the foregoing is directed to embodiments of the present invention,other and further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

EXAMPLES Experimental Methods

Inventive compositions: Sample preparation: Pads and parts.

Compression molding: Approximately 90 g of sample were placed in8″×8″×125/1000″ thick metal frame between two sheets of Mylar in aheated press at 400 deg F. The sample is heated in compression betweentwo metal plates about ½″ thick. The sample is pre heated for 15 minutesthen pressed for 3 minutes at 15,000 psi. The sample is released andcooled under pressure of 2000 to 5000 psi for 4 minutes at 23 deg C.

The pads are removed and aged under controlled temperature and humidityconditions (50% relative humidity, room temperature) for 48 hours beforethe samples are of the testing geometry as specified in the test beloware removed with a die.

MFR: Melt Flow rate was determined according to ASTM D-1238-04C at 230 Cand is reported as g/10 min.

Flex Modulus Flexural modulus is determined as 1% secant according toD-790-0310618-05 and is reported as psi.

Brookfield Viscosity Melt Viscosity was measured according to ASTMD-3236 using a Brookfield Thermosel viscometer at 190 C and are reportedas cps.

DSC Tc, Tm, DeltaHf Peak melting point (Tm) in C, heat of fusion (DeltaHf in J/g), peak crystallization point (Tc) in C were determined usingthe following procedure. Differential scanning calorimetric (DSC) datawas obtained using a TA Instruments model 2920 machine. Samples weighingapproximately 7-10 mg were molded and sealed in aluminum sample pans.After 48 hours at room temperature (21 C to 25 C) the samples areanalyzed. The DSC data was recorded by first cooling the sample to −50°C. and then gradually heating it to 200° C. at a rate of 10° C./minute.This sequence of operation is the first heating cycle. The sample iskept at 200° C. for 5 minutes before a cooling cycle is applied at 10C/minute to −50 C. This is the second cooling cycle. The peak meltingpoint and the heat of fusion is obtained from the first heating cycle.The peak crystallization point is determined from the second coolingcycle.

Tear Resistance: Tear resistance is measured as Die C tear according toTest ASTM D-624 and is reported as the peak force in lb force/in.

Surface Stickiness is measured by touching the molded composition after24 hours of annealing at ambient temperature with the right indexfinger. A non sticky sample is one which does not adhere instantly tothe finger and nor does the removal of the finger leave a visual mark ordistenstion on the surface of the sample.

Tensile Strength and Stress Strain Values. Samples of the inventivecomposition were tested were tested according to ASTM D-638, except thatthe separation of the grips was conducted at 20 inches per minute. Theextension of the grips and thus the samples was independently determinedusing an extensometer attached to the testing apparatus. The tensilestrength data is reported as psi, the elongation is reported as the %elongation of the distension zone of the sample.

Composition of the First Polymer Component: Wt % Ethylene

The ethylene content in polymers can be measured as follows. This methodis designed to measure ethylene content between 5 and 40 wt % ethylene.A thin homogeneous film is pressed according to sub-method A of ASTMD-3900. It is then mounted on a Perkin Elmer Spectrum 2000 infraredspectrophotometer. A full spectrum is recorded using the followingparameters: resolution: 4.0 cm−1, spectral range: 4500 to 450 cm−1.Ethylene content is determined by taking the ratio of the propylene bandarea at 1155 cm−1 to the ethylene band area at 732 cm−1 (C3/C2=AR) andapplying it to the following equation:

Ethylene wt %=82.585-111.987X+30.045X², where X is the ratio of the peakheight at 1155 cm−1 and peak height at either 722 cm−1 or 732 cm−1,whichever is higher.

Composition of the First Polymer Component: Wt % Alpha Olefin Other thanEthylene or Propylene

The CNMR technique for the determination of hexene content inpropylene/hexene copolymers is described in Macromol. Cem. Phys., 201,401, (2000). The procedure involves collecting a CNMR spectrum on apolymer sample that has been dissolved in a solvent(tetrachloroethane-d2) and integrating the spectral intensity. The molepercent hexene can be determined by ratioing of peak integrals whichcorrespond to the number of moles of hexene to the number of moles ofall monomer in the sample.

Molecular Weight of the First Polymer Component: By GPC

Molecular weights (weight average molecular weight (Mw) and numberaverage molecular weight (Mn)) are determined using a Waters 150 SizeExclusion Chromatograph (SEC) equipped with a differential refractiveindex detector (DRI), an online low angle light scattering (LALLS)detector and a viscometer (VIS). The details of the detectorcalibrations have been described elsewhere [Reference: T. Sun, P. Brant,R. R. Chance, and W. W. Graessley, Macromolecules, Vol. 34, No. 19, pp.6812-6820, (2001)]; attached below are brief descriptions of thecomponents.

The SEC with three Polymer Laboratories PLgel 10 mm Mixed-B columns, anominal flow rate 0.5 cm³/min, and a nominal injection volume 300 μL iscommon to both detector configurations. The various transfer lines,columns and differential refractometer (the DRI detector, used mainly todetermine eluting solution concentrations) are contained in an ovenmaintained at 135° C. The LALLS detector is the model 2040 dual-anglelight scattering photometer (Precision Detector Inc.). Its flow cell,located in the SEC oven, uses a 690 nm diode laser light source andcollects scattered light at two angles, 15° and 90°. Only the 15° outputwas used in these experiments. Its signal is sent to a data acquisitionboard (National Instruments) that accumulates readings at a rate of 16per second. The lowest four readings are averaged, and then aproportional signal is sent to the SEC-LALLS-VIS computer. The LALLSdetector is placed after the SEC columns, but before the viscometer.

The viscometer is a high temperature Model 150R (Viscotek Corporation).It consists of four capillaries arranged in a Wheatstone bridgeconfiguration with two pressure transducers. One transducer measures thetotal pressure drop across the detector, and the other, positionedbetween the two sides of the bridge, measures a differential pressure.The specific viscosity for the solution flowing through the viscometeris calculated from their outputs. The viscometer is inside the SEC oven,positioned after the LALLS detector but before the DRI detector.

Solvent for the SEC experiment was prepared by adding 6 grams ofbutylated hydroxy toluene (BHT) as an antioxidant to a 4 liter bottle of1,2,4 Trichlorobenzene (TCB) (Aldrich Reagent grade) and waiting for theBHT to solubilize. The TCB mixture was then filtered through a 0.7 μmglass pre-filter and subsequently through a 0.1 μm Teflon filter. Therewas an additional online 0.7 μm glass pre-filter/0.22 μm Teflon filterassembly between the high pressure pump and SEC columns. The TCB wasthen degassed with an online degasser (Phenomenex, Model DG-4000) beforeentering the SEC.

Polymer solutions were prepared by placing dry polymer in a glasscontainer, adding the desired amount of TCB, then heating the mixture at160° C. with continuous agitation for about 2 hours. All quantities weremeasured gravimetrically. The TCB densities used to express the polymerconcentration in mass/volume units are 1.463 g/ml at room temperatureand 1.324 g/ml at 135° C. The injection concentration ranged from 1.0 to2.0 mg/ml, with lower concentrations being used for higher molecularweight samples.

Prior to running each sample the DRI detector and the injector werepurged. Flow rate in the apparatus was then increased to 0.5 ml/minute,and the DRI was allowed to stabilize for 8-9 hours before injecting thefirst sample. The argon ion laser was turned on 1 to 1.5 hours beforerunning samples by running the laser in idle mode for 20-30 minutes andthen switching to full power in light regulation mode.

The branching index was measured using SEC with an on-line viscometer(SEC-VIS) and are reported as g′ at each molecular weight in the SECtrace. The branching index g′ is defined as: where η_(b) is theintrinsic viscosity of the branched polymer and η₁ is the intrinsicviscosity of a linear polymer of the same viscosity-averaged molecularweight (M_(v)) as the branched polymer. η₁=KM_(v) ^(α), K and α aremeasured values for linear polymers and should be obtained on the sameSEC-DRI-LS-VIS instrument as the one used for branching indexmeasurement. For polypropylene samples presented in this invention,K=0.0002288 and α=0.705 were used. The SEC-DRI-LS-VIS method obviatesthe need to correct for polydispersities, since the intrinsic viscosityand the molecular weight are measured at individual elution volumes,which arguably contain narrowly dispersed polymer. Linear polymersselected as standards for comparison should be of the same viscosityaverage molecular weight and comonomer content. Linear character forpolymer containing C2 to C10 monomers is confirmed by Carbon-13 NMR themethod of Randall (Rev. Macromol. Chem. Phys., C29 (2&3), p. 285-297).

Polymer Components First Polymer Component

The first polymer component was obtained as a variety of low molecularweight, propylene dominant polymers of varying degrees of crystallinity.

Component F.1 (Comparative only) One process for the preparation ofthese polymers by thermal degradation of an identical polymer of highermolecular weight is described in U.S. Pat. No. 6,747,114, which is fullyincorporated herein by reference. In this synthesis 2000 g Vistamaxx6200, available from the Exxon Mobil Chemical Co, Houston, Tex. wasintimately mixed with 20.05 g of Lupersol 101[2,5-bis(tert-butylperoxy)-2,5-dimethyl-hexane], available from AkzoNobel, and was extruded through a 500 mm Twin Screw Extruder with an L/Dof 50. The Twin screw extruder was divided into six thermal sections anda temperature of 250 C was maintained at each. The twin screw extruderwas maintained at 65 rpm and the mixture of the Vistamaxx 6200 and theperoxide was metered in at about 17 g/min. The mean residence time inthe extruder was about 120 seconds and based on an analysis of thedegradation lifetime kinetics of the peroxide this amount of time wasconsidered at the experimental temperature to result in deminimus levelsof the peroxide to be still present in the polymer. The product of theis reaction, component F.1, was collected in silicone lined paper traysand allowed to cool before being separated into smaller pieces forfurther evaluation.

Component F.2 (Inventive) All polymerizations were performed in a liquidfilled, single-stage continuous reactor using mixed metallocene catalystsystems. The reactor was a 0.5-liter stainless steel autoclave reactorand was equipped with a stirrer, water cooling/steam heating elementwith a temperature controller, and a pressure controller. Solvents,propylene, and comonomers (such as hexane and octene) were firstpurified by passing through a three-column purification system. Thepurification system consisted of an Oxiclear column (Model # RGP-R1-500from Labelear) followed by a 5 A and a 3 A molecular sieve columns.Purification columns were regenerated periodically whenever there wasevidence of lower activity of polymerization. Both the 3 A and 5 Amolecular sieve columns were regenerated in-house under nitrogen at aset temperature of 260 C and 315 C, respectively. The molecular sievematerial was purchased from Aldrich. Oxiclear column was regenerated inthe original manufacture. The purified solvents and monomers were thenchilled to about −15 C by passing through a chiller before being fedinto the reactor through a manifold. Solvent and monomers were mixed inthe manifold and fed into reactor through a single tube. All liquid flowrates were measured using Brooksfield mass flow meters or Micro-MotionCoriolis-type flow meters.

The catalyst was rac-dimethylsilylbisindenyl zirconium dimethyl(obtained from Albemarle) (HAFNIUM FOR M1) pre-activated withN,N-dimethylanilinium tetrakis (pentafluorophenyl) (obtained fromAlbemarle) at a molar ratio of about 1:1 in toluene. The catalystsolution was kept in an inert atmosphere with <1.5 ppm water content andwas fed into reactor by a metering pump through a separated line.Catalyst and monomer contacts took place in the reactor.

As an impurity scavenger, 250 ml of tri-n-octyl aluminum (TNOA) (25 wt %in hexane, Sigma Aldrich) was diluted in 22.83 kilogram of hexane. TheTNOA solution was stored in a 37.9-liter cylinder under nitrogenblanket. The solution was used for all polymerization runs until about90% of consumption, then a new batch was prepared. Pumping rates of theTNOA solution varied from polymerization reaction to reaction, rangingfrom 0 (no scavenger) to 4 ml per minutes.

The reactor was first cleaned by continuously pumping solvent (e.g.,hexane) and scavenger through the reactor system for at least one hourat a maximum allowed temperature (about 150 C). After cleaning, thereactor was heated/cooled to the desired temperature using a water/steammixture flowing through the reactor jacket and controlled at a setpressure with controlled solvent flow. Monomers and catalyst solutionswere then fed into the reactor when a steady state of operation wasreached. An automatic temperature control system was used to control andmaintain the reactor at a set temperature. Onset of polymerizationactivity was determined by observations of a viscous product and lowertemperature of water-steam mixture. Once the activity was establishedand the system reached equilibrium, the reactor was lined out bycontinuing operating the system under the established condition for atime period of at least five times of mean residence time prior tosample collection. The resulting mixture, containing mostly solvent,polymer and unreacted monomers, was collected in a collection box afterthe system reached a steady state operation. The collected samples werefirst air-dried in a hood to evaporate most of the solvent, and thendried in a vacuum oven at a temperature of about 90 C for about 12hours. The vacuum oven dried samples were weighed to obtain yields. Allthe reactions were carried out at a pressure of about 2.41 MPa-g.

Component F.2 (inventive) Component F.2 is an inventive propyleneethylene copolymer having a isotactic propylene crystallinity made bythe copolymerization of the comonomer in solution polymerization.Different versions of F.2 which differ in their molecular weight (andthus viscosity) and the content of hexene (and thus the crystallinity)are differentiated in this these specification by a subscript Romannumeral at the end of this class F.2. Thus different polymers areindicated as F.2.1, F.2.2 in Table 3.

TABLE 3 Component F.2 composed of Propylene and ethylene Yield ViscosityRxr C3 C2 Catalyst (gram/ delta @190 C. Ethylene Sample Temp (g/min)(SLPM) #1 min) Tc (C.) Tm (C.) Tg (C.) H (J/g) (cp) (wt %) F.2.1 85 140.5 M1/D4 10.93 27.43 78.39 −20.81 44.99 2791 4.6 F.2.2 70 14 0.7 M1/D414.30 37.34 81.86 −23.26 38.22 80500 7.5 F.2.3 70 14 0.8 M1/D4 14.7829.01 76.38 −26.70 43.96 76600 7.7 F.2.4 80 14 0.7 M1/D4 15.00 31.7779.30 −25.65 47.08 15450 7.2 F.2.5 75 14 0.7 M1/D4 13.80 35.32 82.47−19.81 36.01 36000 8.9 F.2.6 75 14 0.8 M1/D4 13.90 27.75 77.01 −21.8531.97 30800 9.84 F.2.7 80 14 1.2 M1/D4 15.15 17.73 59.38 −26.94 10.0427260 12.9 F.2.8 80 14 1.5 M1/D4 15.33 — — −27.89 Na 34000 16 F.2.9 7014 1 M1/D4 11.85 10.02 62.16 −25.20 21.71 74400 11.9 F.2.10 70 14 1.2M1/D4 12.65 21.32 57.94 −27.40 12.57 107000 13.6 F.2.11 70 14 1.5 M1/D410.50 — — −30.68 — 175000 17.7 F.2.12 80 14 1 M1/D4 13.75 52.24 98.63−25.61 31.98 18600 10.7 F.2.13 90 14 1.2 M1/D4 10.58 — — −28.84 Na 4355011.7 F.2.14 90 14 1.4 M1/D4 10.00 — — −31.75 — 67600 14.2 F.2.15 80 140.6 M1/D9 11.83 43.43 88.37 −22.94 49.25 na 6.1 F.2.16 85 14 1.2 M1/D412.0 26.2  59.7  −28.7 6   41000 14.5 F.2.17 80 14 1.2 M1/D4 11.28 Na59.19 −28.73  6.19 111000 14.3 F.2.18 53   250000

Comparative experiments with blends were also run with component F.3(comparative polymer) which is Vistamaxx 6100 from the ExxonMobilChemical co, Houston, Tex. Component F.3 has 16.4% ethylene content andan Mw (weight average) by GPC of 221000.

F.4 is a comparative polymer sample of atactic propylene hexenecopolymer containing 6 wt % hexene and having a Brookfield viscosity of12000 cps at 190 C.

Second Polymer Component

The second Polymer component (Component S hereinafter) was obtained fromExxonMobil Chemical Company, Houston, Tex. as Polypropylene of variousmolecular weights and crystallinities as denoted below

Component S.1 is Escorene PP4712, a Ziegler-Natta homoisotactic iPP withMFR of 3.1 g/10 min.

Component S.2 is Escorene PP3155, a Ziegler-Natta homopolymer iPP withMFR of 35 g/10 min.

Component S.3 is Escorene PP2252, a Ziegler-Natta homopolymer iPP withMFR of 3 g/10 min.

Component S.4 is Escorene PP9302E1 a Ziegler Natta copolymer ofpropylene and ethylene of 3 g/10 min MFR with approximately 4 wt % C2.

Component S.5 is Escorene PP Copolymer 9122, a Ziegler Natta copolymerof propylene and ethylene of 2 g/10 min MFR with approximately 2 wt %C2.

Component S.6 is Escorene PP 8244 which is an impact copolymercontaining about 30% ethylene propylene rubber plus plastomer.

Plasticizer Hereinafter Component P

Component P is Sunpar 150 plasticizer oil, available form the SunChemical Co, Marcus Hook, Pa.

Component P.1 is Tufflo 6056, a plasticizer oil.

Component P.2 is tackifier PR100A, a cyclic olefin oligomer, availablefrom ExxonMobil Chemical Co, Houston Tex.

Component P.3 is atactic polypropylene, plasticizer oil, 24227-105-5.

In all subsequent examples compositions of the blend are expressed ingrams of each component which are blended together.

Example 1- 1 2 3 4 5 6 7 8 9 10 Compositions F.3 0.0 12.5 25.0 50.0 75.0100.0 125.0 137.5 150.0 162.5 S.1 250.0 237.5 225.0 200.0 175.0 150.0125.0 112.5 100 87.5 Properties Flexural Modulus (1% 224 177 1717 128793 55 31 20 sec), 10³ psi Young's Modulus, 1581.5 1239 1226 1696 655.3391.4 234 (MPa) Tensile elongation @20″/ min at 23 C. (psi) Modulus at50% * * * 2529.1 2351.4 1956.2 1293.6 1117.4 889.7 650.5 elongationModulus at 100% * * * 2016.0 2145.3 1960.9 1410.3 1208 1003.6 760.7elongation Modulus at 200% * * * * * 1858.1 1548.3 1329.5 1174.8 957.1elongation Modulus at 500% * * * * * * 1734.6 1643 1544.9 1401.1elongation Ultimate Elongation (%) * * * 125.0 110.0 400.0 729.6 749.2842.9 787.0 Ultimate tensile (psi) 5067.0 5059.2 4428.2 3735.7 2638.51970.7 2005.0 2098.3 2157.7 1981.7

Example 2- 1 2 3 4 5 6 7 8 Compositions F.1 200 300 400 500 300 600 680770 S.2 1000 1000 1000 950 1000 900 800 730 C 200 200 200 200 400 200200 200 Properties yield elongation % 3 8.9 11.2 14.3 4.8 18.09 30.425.7 yield tensile strength, (psi) 1439 2149 2149 1723 1167 1661 14821055 elongation (break), % 2.9 8.9 11.2 14.3 4.8 22.7 100.3 97.0 tensilestrength (break), psi 1439 2149 2149 1723 1167 1703 1482 1055 Tear Die Clb/in 110 206 214 225 82 270.1 333 296 1% sec modulus (10³ psi) 71.663.2 62.1 48.8 42.8 36.9 25 16.6

Example 3 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Com- position F.1 43 60 7591 106 121 136 60 75 91 90 82 74 68 68 S.3 214 200 188 173 159 143 129159 159 159 100 100 100 119 110 C 43 40 38 36 35 36 35 35 35 35 36 44 5238 50 Properties yield 22.8 23.6 32.5 37.5 39.2 29.8 29.1 35.8 45.2 48.834.2 33.7 32.8 elongation % yield 2065 2038 1735 1420 1236 1748 17381622 1232 1203 1389 1662 1398 tensile strength, (psi) elongation 32.759.0 261.3 343.6 403.0 32.7 43.0 117.7 420.0 316.7 44.3 51.7 56.0(break), % tensile 2065 2038 1735 1420 1199 1748 1738 1738 1235 12031369 1662 1398 strength (break), psi Tear Die 296 405 423 329 329 259302 386 352 357 377 440 353 C lb/in Youngs 255 303 247 182 117 219 218211 134 116 174 198 166 Mod (MPa) 1% sec 36.8 42.6 34.7 25.3 16.9 30.831.3 29.7 19.1 16.8 25.2 28.3 23.9 modulus (10³ psi)

All of the compositions in Example 4 were sticky to the surface touchand left an adherent layer of polymer during pressing between Mylarsheets.

Example 4 1 2 3 4 5 Composition F.4 69 68 68 69 69 A3 130 119 110 140156 C 27 38 50 16 0 Properties yield elongation % 30 38.7 38 23.2 yieldtensile strength, (psi) 1660 1272 1780 2286 elongation (break), % 39038.7 689 617 tensile strength (break), psi 1651 127 2 2360 2158 Tear DieC lb/in 397 236 472 578 Youngs Mod (MPa) 176 141 228 361 1% sec modulus(10³ psi) 25.3 20 32.5 51.8

Example 5- 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Composition F.2.18 6968 68 69 F.2.1 69 68 F.2.2 69 68 F.2.3 69 68 F.2.4 69 68 F.2.5 69 68F.2.6 69 68 A3 130 119 110 156 156 119 156 119 156 119 156 119 156 119156 119 C 27 38 50 0 0 38 0 38 0 38 0 38 0 38 0 38 Properties yieldelongation % 37 47 50 25 28 30 59 28 58 31 56 29 61 31 62.5 yieldtensile strength, (psi) 2914 2571 2058 4237 3661 3781 2058 3486 20633724 2077 3732 2199 3915 2007 elongation (break), % 758 736 595 396 7524 279 87 202 1026 149 71 131 265 210 438 tensile strength (break), psi2345 2058 1976 2470 1837 1623 2007 1755 1946 1907 2106 2009 2064 18662089 1808 Tear Die C lb/in 614 550 461 684 502 683 389 794 509 254 667358 710 710 353 Youngs Mod (MPa) 607 479 391 1038 822 823 323 787 314806 300 817 327 797 298 1% sec modulus (10³ psi) 85 66 54 144 113 114 44109 43 113 41 114 45 110 40 MFR @ 230 C. g/10 min 23 30 40 10 32 179 1671 16 55 21 98 22 92 19 96 Crystallization time (min) 0.23 0.07 0.23

Example 6- 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Composition F.2.15 69 68F.2.7 69 68 F.2.8 69 68 F.2.9 69 68 F.2.10 69 68 F.2.11 69 68 F.2.12 6968 A3 156 119 156 156 156 156 156 119 119 119 119 119 156 119 C 0 38 0 00 0 0 38 38 38 38 38 0 38 Properties yield 28 55 36 31 31 23 18 45 35 6060 58 25 33 elongation % yield tensile 3865 2167 3416 3082 3458 32202909 1709 1479 1938 1748 1465 3703 1841 strength, (psi) elongation 758945 254 128 309 154 361 69 43 744 862 75 54 41 (break), % tensilestrength 2367 2304 2181 2457 2323 2400 2329 1646 1420 1882 1895 16752318 1793 (break), psi Tear Die C lb/in 754 519 654 671 715 706 736 287229 516 488 404 634 233 Youngs Mod 829 352 749 713 794 875 886 252 265282 236 289 886 313 (MPa) 1% sec modulus 117 48 104 99 111 122 124 35 3639 33 40 124 43 (10³ psi) MFR @ 230 C. 11 41 17 21 70 16 92 96 56 51 4829 104 g/10 min Crystallization 0.083 0.05 0.083 0.05 0.25 0.22 0.23 0.20.117 0.28 time (min)

Example 7- 1 2 3 4 5 6 7 8 9 10 11 Composition F.2.17 81 90 90 72 81 8163 90 72 81 S.3 7 108 108 108 S.4 101 108 90 108 108 108 117 117 C 36 270 27 45 36 27 45 27 45 36 Properties elongation (break), % 398 1443 9611443 573 1097 1037 509 156 54 75 tensile strength (break), psi 968 1325780 1325 975 1094 1193 964 1191 1242 935 Tear Die C lb/in 292 345 263345 294 318 355 329 346 182 233 1% sec modulus (10³ psi) 8 9 7 9 8 8 1110 20 18 18 MFR @230 C. g/10 min 73 73 90 80 69 78 88 132 116Crystallization time (min) 2.3 4.5 1.8 4.5 5.8 5.8 4.3 4.2 0.3 0.3 0.3

Example 8- 1 2 3 4 5 6 7 8 Composition F.1 68 54 81 81 90 72 54 54 S.4119 135 108 138 122 135 126 144 C 38 36 36 6 14 18 45 27 Propertieselongation (break), % 508 1151 1298 1372 1377 99 1229 1566 tensilestrength (break), psi 1068 1526 1123 1547 1442 1252 1464 1865 Tear Die Clb/in 395 429 350 485 411 469 377 488 1% sec modulus (10³ psi) 11 19 1024 17 22 13 23 MFR @ 230 C. g/10 min 94 65 129 60 85 59 91 53Crystallization time (min) 6.2 4.6 4.6 2.2 2.3 2.7 7 3.3 Example 8- 9 1011 12 13 14 15 16 Composition F.1 63 63 63 72 72 72 81 90 S.4 117 126135 108 117 126 117 108 C 45 36 27 45 36 27 27 27 Properties elongation(break), % 621 1142 1330 1197 901 1159 1479 1312 tensile strength(break), 1120 1368 1623 1198 1227 1485 1442 1207 psi Tear Die C lb/in378 398 427 317 336 410 386 338 1% sec modulus (10³ psi) 10 15 19 9 1015 12 10 MFR @ 230 C. g/10 min 121 98 74 140 103 91 48 140Crystallization time 5.2 3.9 3.2 4.9 4.2 3.4 3.8 3.1 (min)

Example 9- 1 2 3 4 5 6 F.2.12 68 68 F.2.13 68 68 F.2.14 68 68 S4 156 119156 119 156 119 C 0 38 0 38 0 38 yield elongation % 46 92 38 103 45 74yield tensile 1898 1083 1795 1027 2090 1208 strength, (psi) elongation1041 782 1534 825 853 607 (break), % tensile strength 1685 1229 18941215 1775 1263 (break), psi Tear Die C lb/in 609 363 564 341 646 399 1%sec modulus 33 12 38 12 41 15 (10³ psi) MFR @ 230 C. 14 51 12 48 11 53g/10 min Crystallization 2 3.8 1.7 4 2.3 3.5 time (min)

Example 10- 1 2 3 4 F.2.8 69 68 69 68 S3 0 0 156 119 S4 156 119 C 0 18 038 yield elongation % 44 71 31 35 yield tensile strength, (psi) 20111374 3082 1479 elongation (break), % 189 412 128 43 tensile strength(break), psi 1512 1271 2457 1420 Tear Die C lb/in 606 441 671 229 1% secmodulus (10³ psi) 30 18 99 36 MFR @ 230 C. g/10 min 14 44 21 92Crystallization time (min) 1.5 2.4 0.05 0.22

Example 11- 1 2 3 4 5 6 7 8 9 10 11 Composition F.2.16 90 11 11 11 79 7979 128 128 S.4 214 146 S.5 225 214 146 S.6 108 225 214 146 70 70 P.1 27Properties elongation (break), % 142 38 22 47 24 103 199 91 1055 577 186tensile strength (break), psi 645 3527 2232 1839 1714 1843 1684 10801696 707 346 Tear Die C lb/in 211 821 489 776 427 740 651 291 605 270171 1% sec modulus (10³ psi) 12 154 115 130 92 86 48 35 34 9 4 MFR @ 230C. g/10 min Crystallization time (min) 0.42 1.3 0.98 1.6 3 0.25 0.18

Example 12 1 2 3 4 5 6 7 Composition F.2.16 90 90 90 90 90 90 83 S.4 108108 108 108 108 S.5 108 108 C 27 27 27 27 27 27 27 Properties elongation1323 1147 1354 978 1597 1375 836 (break), % tensile strength 1421 13031424 1310 1633 1562 1258 (break), psi Tear Die C lb/in 377 425 388 396387 407 382 1% sec modulus 12 13 11 12 11 16 13 (10³ psi)Crystallization 3 0.9 1.2 time (min) Injection molding conditions forinventive compositions

Mixing done on 0° C. Mixer in Area M

Used NESSEI lab injection molding machine in PSL

Sample −1 −2 −3 −4 Mixing Time (min) 5 5 5 5 Temperature (F) 382 383 370396 End Temp. (F) 397 378 367 390 Injection Molding Mold Temp. (F) 120120 120 120 Nozzle Temp (F) 392 392 392 392 Barrel Temp. (F) 374 374 374374 Tensile Boost (s) 1.5 1.5 1.6 1.5 Cushion (mm) 9.2 9.9 9.4 7.8 FlexBoost (s) 1.5 1.5 1.6 1.5 Cushion (mm) 7.8 7.9 8.3 9.7

1. A heterogeneous blend composition comprising: a. from 1% to 99% byweight of the blend of a first polymer component comprising a copolymerof 5% to 35% by weight of the first polymer component consisting ofethylene derived units and 65% to 95% by weight of the first polymercomponent of propylene derived units having a crystallinity of 0.1% toabout 25% from isotactic polypropylene sequences, a melting point offrom 45° C. to 105° C., and wherein the Melt Flow Rate (MFR@230 C) ofthe first polymer component is between 300 g/10 min to 5000 g/10 min andb. from 1% to 99% by weight of the blend of a propylene polymercomponent comprising random copolymers of propylene, wherein thepercentage of the copolymerized alpha-olefin in the copolymer is between0 and 9% by weight of the second polymer component and wherein thesecond polymer component has a melting point greater than about 110° C.,wherein the first polymer component has less than 1000 ppm of reactionproducts arising from the chemical reaction of a molecular degradationagent.; wherein the heterogeneous blend composition has a meltingtemperature greater than about 90° C.
 2. The heterogeneous blendcomposition of claim 1, wherein the propylene polymer component has aMelt Flow Rate (ASTM D-1238) less than 10 g/10 min.
 3. The heterogeneousblend composition of claim 1, wherein the first polymer component has acrystallinity of 3% to 10% from isotactic polypropylene sequences. 4.The heterogeneous blend composition of claim 1, wherein the firstpolymer component further comprises less than 10 wt. % of anon-conjugated diene.
 5. The heterogeneous blend composition of claim 1,wherein the first polymer component is made with a polymerizationcatalyst which forms isotactic polypropylene and the second polymercomponent has isotactic propylene sequences.
 6. The heterogeneous blendcomposition of claim 1, wherein the heterogeneous blend composition hasa melting temperature greater than about 100° C.
 7. The heterogeneousblend composition of claim 1, wherein the heterogeneous blendcomposition has a melting temperature greater than about 110° C.
 8. Theheterogeneous blend composition of claim 1, wherein the heterogeneousblend composition has a melting temperature greater than about 125° C.